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| United States Patent Application |
20010023515
|
| Kind Code
|
A1
|
|
Cottard, Francois
;   et al.
|
September 27, 2001
|
Compositions for oxidation dyeing keratin fibers comprising at least one
oxidation dye, at least one thickening polymer comprising at least one
fatty chain, and at least one fatty alcohol comprising more than twenty
carbon atoms and uses thereof
Abstract
Compositions for oxidation dyeing keratin fibers, such as human keratin
fibers like hair, comprising, in a dyeing medium, (1) at least one
oxidation dye, (2) at least one thickening polymer comprising at least
one fatty chain, and (3) at least one fatty alcohol comprising more than
twenty carbon atoms. Processes comprising such oxidation dyeing
compositions.
| Inventors: |
Cottard, Francois; (Levallois-Perret, FR)
; Rondeau, Christine; (Sartrouville, FR)
|
| Correspondence Address:
|
Thomas L. Irving
FINNEGAN, HENDERSON, FARABOW
GARRETT & DUNNER, L.L.P.
1300 I Street, N.W.
Washington
DC
20005-3315
US
|
| Serial No.:
|
750718 |
| Series Code:
|
09
|
| Filed:
|
January 2, 2001 |
| Current U.S. Class: |
8/406; 8/421 |
| Class at Publication: |
8/406; 8/421 |
| International Class: |
A61K 007/13 |
Foreign Application Data
| Date | Code | Application Number |
| Dec 30, 1999 | FR | 99 16762 |
Claims
What is claimed is:
1. A cosmetic composition for oxidation dyeing keratin fibers, comprising,
in a dyeing medium (1) at least one oxidation dye, (2) at least one
thickening polymer comprising at least one fatty chain, and (3) at least
one fatty alcohol comprising more than twenty carbon atoms.
2. A composition according to claim 1, wherein said keratin fibers are
chosen from human keratin fibers.
3. A composition according to claim 2, wherein said human keratin fibers
are chosen from human hair.
4. A composition according to claim 1, wherein said at least one fatty
alcohol comprising more than twenty carbon atoms is chosen from behenyl
alcohol.
5. A composition according to claim 1, wherein said at least one fatty
alcohol comprising more than twenty carbon atoms is chosen from erucyl
alcohol.
6. A composition according to claim 1, wherein said at least one fatty
alcohol is a mixture of fatty alcohols comprising at least 30% by weight
of at least one fatty alcohol comprising more than twenty carbon atoms.
7. A composition according to claim 1, wherein said at least one fatty
alcohol comprising more than twenty carbon atoms is present in an amount
ranging from 0.01% to 30% by weight relative to the total weight of the
composition.
8. A composition according to claim 7, wherein said at least one fatty
alcohol comprising more than twenty carbon atoms is present in an amount
ranging from 0.05% to 20% by weight relative to the total weight of the
composition.
9. A composition according to claim 8, wherein said at least one fatty
alcohol comprising more than twenty carbon atoms is present in an amount
ranging from 0.1% to 15% by weight relative to the total weight of the
composition.
10. A composition according to claim 1, wherein said at least one
thickening polymer comprising at least one fatty chain is chosen from
anionic, nonionic and cationic thickening polymers comprising at least
one fatty chain.
11. A composition according to claim 10, wherein said anionic thickening
polymers comprising at least one fatty chain comprise at least one
hydrophilic unit and at least one allyl ether unit comprising at least
one fatty chain.
12. A composition according to claim 11, wherein said at least one
hydrophilic unit is chosen from ethylenic unsaturated anionic monomeric
residues.
13. A composition according to claim 12, wherein said ethylenic
unsaturated anionic monomeric residues are chosen from residues of
vinylcarboxylic acid.
14. A composition according to claim 11, wherein said at least one allyl
ether unit comprising at least one fatty chain is chosen from monomeric
residues formed from monomers of formula (I): CH.sub.2.dbd.C--R'--CH.sub.-
2--O--B.sub.n--R (I) in which R' is chosen from H and CH.sub.3, B is an
ethyleneoxy group, n is chosen from zero and integers ranging from 1 to
100, R is a hydrocarbon group chosen from alkyl, arylalkyl, aryl,
alkylaryl and cycloalkyl groups, comprising from 8 to 30 carbon atoms.
15. A composition according to claim 14, wherein said hydrocarbon group
comprises from 10 to 24 carbon atoms.
16. A composition according to claim 15, wherein said hydrocarbon group
comprises from 12 to 18 carbon atoms.
17. A composition according to claim 10, wherein said anionic thickening
polymers comprising at least one fatty chain comprise at least one
hydrophilic unit of the olefinic unsaturated carboxylic acid type and at
least one hydrophobic unit of the (C.sub.10-C.sub.30)alkyl ester of
unsaturated carboxylic acid type.
18. A composition according to claim 17, wherein said at least one
hydrophilic unit of the olefinic unsaturated carboxylic acid type is
chosen from monomeric residues formed from monomers of formula (II):
22in which R.sub.1 is chosen from H, CH.sub.3, and C.sub.2H.sub.5, and
wherein said at least one hydrophobic unit of the (C.sub.10-C.sub.30)alky-
l ester of unsaturated carboxylic acid type is chosen from monomeric
residues formed from monomers of formula (III): 23in which R.sub.2 is
chosen from H, CH.sub.3, and C.sub.2H.sub.5, and R.sub.3 is chosen from
C.sub.10-C.sub.30 alkyl groups.
19. A composition according to claim 18, wherein said R.sub.3 is chosen
from C.sub.12-C.sub.22 alkyl groups.
20. A composition according to claim 10, wherein said anionic thickening
polymers comprising at least one fatty chain are chosen from terpolymers
of maleic anhydride/C.sub.30-C.sub.38 .alpha.-olefin/alkyl maleate.
21. A composition according to claim 10, wherein said anionic thickening
polymers comprising at least one fatty chain are chosen from acrylic
terpolymers comprising: (a) a carboxylic acid with
.alpha.,.beta.-monoethylenic unsaturation (b) a nonsurfactant monomer
with .alpha.,.beta.-monoethylenic unsaturation different from (a) (c) a
nonionic monourethane which is the product of the reaction of a
monohydric surfactant with a monoisocyanate with monoethylenic
unsaturation.
22. A composition according to claim 10, wherein said anionic thickening
polymers comprising at least one fatty chain are chosen from copolymers
formed from at least two monomers, wherein at least one of said at least
two monomers is chosen from a carboxylic acid with
.alpha.,.beta.-monoethylenic unsaturation, an ester of a carboxylic acid
with .alpha.,.beta.-monoethylenic unsaturation, and an oxyalkylenated
fatty alcohol.
23. A composition according to claim 10, wherein said nonionic thickening
polymer comprising at least one fatty chain is chosen from: (1)
celluloses modified by at least one group comprising at least one fatty
chain; (2) hydroxypropylguars modified by at least one group comprising
at least one fatty chain; (3) copolymers formed from vinylpyrrolidone and
at least one hydrophobic monomer comprising at least one fatty chain; (4)
copolymers formed from at least one C.sub.1-C.sub.6 alkyl methacrylate
and at least one amphiphilic monomer comprising at least one fatty chain
and copolymers formed from at least one C.sub.1-C.sub.6 alkyl acrylate
and at least one amphiphilic monomer comprising at least one fatty chain;
(5) copolymers formed from at least one hydrophilic methacrylate and at
least one hydrophobic monomer comprising at least one fatty chain and
copolymers formed from at least one hydrophilic acrylate and at least one
hydrophobic monomer comprising at least one fatty chain; (6)
polyether-polyurethanes comprising in their chain both hydrophilic
sequences and hydrophobic sequences; and (7) polymers comprising an
aminoplast ether backbone possessing at least one fatty chain.
24. A composition according to claim 10, wherein said nonionic thickening
polymers are chosen from polyether-polyurethanes comprising at least two
lipophilic hydrocarbon chains, comprising from 6 to 30 carbon atoms,
separated by a hydrophilic sequence, wherein said hydrocarbon chains are
chosen from pendant chains and chains at the end of a hydrophilic
sequence.
25. A composition according to claim 10, wherein said nonionic thickening
polymers are chosen from polyether-polyurethanes comprising a polyblock
sequence.
26. A composition according to claim 25, wherein said
polyether-polyurethanes are in tri-block form.
27. A composition according to claim 10, wherein said cationic thickening
polymers comprising at least one fatty chain are chosen from quaternized
cellulose derivatives and polyacrylates comprising noncyclic
amine-containing side groups.
28. A composition according to claim 1, wherein said at least one
thickening polymer comprising at least one fatty chain is present in an
amount ranging from 0.01% to 10% by weight relative to the total weight
of the composition.
29. A composition according to claim 28, wherein said at least one
thickening polymer comprising at least one fatty chain is present in an
amount ranging from 0.1% to 5% by weight relative to the total weight of
the composition.
30. A composition according to claim 1, wherein said at least one
oxidation dye is chosen from oxidation bases, oxidation couplers, and
their acid addition salts.
31. A composition according to claim 1, wherein said at least one
oxidation dye is chosen from oxidation bases.
32. A composition according to claim 31, wherein said oxidation bases are
chosen from ortho- and para-phenylenediamines, double bases, ortho- and
para-aminophenols, heterocyclic bases, and acid addition salts of any of
the foregoing.
33. A composition according to claim 32, wherein said
para-phenylenediamines are chosen from compounds of formula (I):
24wherein: R.sub.1 is chosen from hydrogen, C.sub.1-C.sub.4 alkyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, polyhydroxy(C.sub.2-C.sub.4
alkyl) groups, (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups,
phenyl groups, 4'-aminophenyl groups, and C.sub.1-C.sub.4 alkyl groups
substituted with at least one group chosen from nitrogen-containing
groups, R.sub.2 is chosen from hydrogen, C.sub.1-C.sub.4 alkyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, polyhydroxy(C.sub.2-C.sub.4
alkyl) groups, (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups, and
C.sub.1-C.sub.4 alkyl groups substituted with a nitrogen-containing
group; R.sub.1 and R.sub.2 may also form, together with the nitrogen atom
to which they are bonded, a 5- or 6-membered nitrogen-containing
heterocycle ring, optionally substituted with at least one group chosen
from alkyl groups, hydroxyl groups and ureido groups; R.sub.3 is chosen
from hydrogen, halogens, C.sub.1-C.sub.4 alkyl groups, sulfo groups,
carboxyl groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
hydroxy(C.sub.1-C.sub.4 alkyoxy) groups, acetylamino(C.sub.1-C.sub.4
alkoxy) groups, mesylamino(C.sub.1-C.sub.4 alkoxy) groups, and
carbamoylamino(C.sub.1-C.sub.4 alkoxy) groups; and R.sub.4 is chosen from
hydrogen, halogens, and C.sub.1-C.sub.4 alkyl groups.
34. A composition according to claim 33, wherein said R.sub.3 is chlorine.
35. A composition according to claim 32, wherein said double bases are
chosen from compounds of formula (II): 25wherein: Z.sub.1 and Z.sub.2,
which may be identical or different, are each chosen from hydroxyl
groups, and --NH.sub.2 groups, optionally substituted with a group chosen
from C.sub.1-C.sub.4 alkyl groups, and linkers Y; linker Y is chosen from
linear and branched, divalent alkylene groups comprising from 1 to 14
carbon atoms, optionally interrupted by, or optionally terminating with,
at least one entity chosen from nitrogen-containing groups and
heteroatoms, and optionally substituted with at least one group chosen
from hydroxyl groups, and C.sub.1-C.sub.6 alkoxy groups; R.sub.5 and
R.sub.6, which may be identical or different, are each chosen from
hydrogen, halogens, C.sub.1-C.sub.4 alkyl groups, monohydroxy(C.sub.1-C.s-
ub.4 alkyl) groups, polyhydroxy(C.sub.2-C.sub.4 alkyl) groups,
amino(C.sub.1-C.sub.4 alkyl) groups, and linkers Y; and R.sub.7, R.sub.8,
R.sub.9, R.sub.10, R.sub.11, and R.sub.12, which may be identical or
different, are each chosen from hydrogen, linkers Y, and C.sub.1-C.sub.4
alkyl groups; provided that said compounds of formula (II) comprise only
one linker Y per molecule.
36. A composition according to claim 35, wherein said heteroatoms are
chosen from oxygen, sulfur, and nitrogen.
37. A composition according to claim 33, wherein said nitrogen-containing
groups are chosen from amino, mono(C.sub.1-C.sub.4)alkylamino,
(C.sub.1-C.sub.4)dialkylamino, (C.sub.1-C.sub.4)trialkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium and ammonium
radicals.
38. A composition according to claim 35, wherein said nitrogen-containing
groups are chosen from amino, mono(C.sub.1-C.sub.4)alkylamino,
(C.sub.1-C.sub.4)dialkylamino, (C.sub.1-C.sub.4)trialkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium and ammonium
radicals.
39. A composition according to claim 32, wherein said para-aminophenols
are chosen from compounds of formula (III): 26wherein: R.sub.13 is
chosen from hydrogen, halogens, C.sub.1-C.sub.4 alkyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, (C.sub.1-C.sub.4)alkoxy(C.sub.-
1-C.sub.4)alkyl groups, amino(C.sub.1-C.sub.4 alkyl), and
hydroxy(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4 alkyl) groups;
R.sub.14 is chosen from hydrogen, halogens, C.sub.1-C.sub.4 alkyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, polyhydroxy(C.sub.2-C.sub.4
alkyl) groups, amino(C.sub.1-C.sub.4 alkyl) groups, cyano(C.sub.1-C.sub.4
alkyl) groups, and (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups.
40. A composition according to claim 39, wherein said halogens are
fluorine.
41. A composition according to claim 32, wherein said heterocyclic bases
are chosen from pyridine derivatives, pyrimidine derivatives,
pyrazolopyrimidine derivatives, and pyrazole derivatives.
42. A composition according to claim 31, wherein said oxidation bases are
present in an amount ranging from 0.0005% to 12% by weight relative to
the total weight of the composition.
43. A composition according to claim 30, wherein said oxidation couplers
are chosen from meta-phenylenediamines, meta-aminophenols,
meta-diphenols, heterocyclic couplers, and their acid addition salts.
44. A composition according to claim 30, wherein said oxidation couplers
are present in an amount ranging from 0.0001% to 10% by weight relative
to the total weight of the composition.
45. A composition according to claim 30, wherein said acid addition salts
are chosen from hydrochlorides, hydrobromides, sulfates, tartrates,
lactates, and acetates.
46. A composition according to claim 1 further comprising at least one
direct dye.
47. A composition according to claim 1 further comprising at least one
reducing agent.
48. A composition according to claim 47, wherein said at least one
reducing agent is present in an amount ranging from 0.05% to 3% by weight
relative to the total weight of the composition.
49. A composition according to claim 1 further comprising at least one
fatty alcohol comprising at most twenty carbon atoms.
50. A composition according to claim 49, wherein said at least one fatty
alcohol comprising at most twenty carbon atoms is present in an amount
ranging from 0.001% to 20% by weight relative to the total weight of the
composition.
51. A ready-to-use cosmetic composition for oxidation dyeing keratin
fibers, wherein said ready-to-use cosmetic composition is obtained by
including at least one composition (A) in a dyeing medium, comprising: at
least one oxidation dye, at least one thickening polymer comprising at
least one fatty chain, and at least one fatty alcohol comprising more
than twenty carbon atoms, with at least one composition (B) comprising at
least one oxidizing agent.
52. A composition according to claim 51, wherein said at least one
oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali
metal bromates, alkali metal ferricyanides, persalts, and
oxidation-reduction enzymes.
53. A composition according to claim 52, wherein said oxidation-reduction
enzymes are chosen from laccases, peroxidases, and oxidoreductases
comprising 2 electrons.
54. A composition according to claim 52, wherein said at least one
oxidizing agent is hydrogen peroxide.
55. A composition according to claim 54, wherein said hydrogen peroxide is
present in an oxygenated water solution comprising a titre ranging from 1
to 40 in volume.
56. A composition according to claim 1, wherein said composition possesses
a pH ranging from 4 to 12.
57. A composition according to claim 51, wherein said keratin fibers are
chosen from human keratin fibers.
58. A composition according to claim 57, wherein said human keratin fibers
are chosen from human hair.
59. A cosmetic composition according to claim 51 further comprising at
least one polymer chosen from cationic polymers and amphoteric polymers,
wherein said at least one polymer is present in said at least one
composition (A), in said at least one composition (B), or in said at
least one composition (A) and said at least one composition (B).
60. A composition according to claim 59, wherein said at least one polymer
is chosen from cationic polymers chosen from quaternary polyammoniums
comprising recurring units of formula (W): 27
61. A composition according to claim 59, wherein said at least one polymer
is chosen from cationic polymers chosen from quaternary polyammoniums
comprising recurring units of formula (U): 28
62. A composition according to claim 59, wherein said at least one polymer
is chosen from amp
hoteric polymers chosen from copolymers comprising at
least one monomeric residue chosen from acrylic acid residue and a
residue of a salt of dimethyldiallylammonium.
63. A composition according to claim 59, wherein said at least one polymer
chosen from cationic polymers and amphoteric polymers is present in an
amount ranging from 0.01% to 10% by weight, relative to the total weight
of the composition.
64. A composition according to claim 63, wherein said at least one polymer
chosen from cationic polymers and amp
hoteric polymers is present in an
amount ranging from 0.05% to 5% by weight relative to the total weight of
the composition.
65. A composition according to claim 64, wherein said at least one polymer
chosen from cationic polymers and amphoteric polymers is present in an
amount ranging from 0.1% to 3% by weight relative to the total weight of
the composition.
66. A composition according to claim 51 further comprising at least one
surfactant chosen from anionic, cationic, nonionic and amp
hoteric
surfactants, wherein said at least one surfactant is present in said at
least one composition (A), in said at least one composition (B), or in
said at least one composition (A) and said at least one compostion (B).
67. A composition according to claim 66, wherein said at least one
composition (A) comprises at least one nonionic surfactant.
68. A composition according to claim 66, wherein said at least one
surfactant is present in an amount ranging from 0.01% to 40% by weight
relative to the total weight of the composition.
69. A composition according to claim 68, wherein said at least one
surfactant is present in an amount ranging from 0.1% to 30% by weight
relative to the total weight of the composition.
70. A composition according to claim 51, wherein at least one thickening
agent chosen from cellulose derivatives, guar derivatives, gums of
microbial origin, and synthetic thickeners which do not possess a fatty
chain is present in said at least one composition (A), in said at least
one composition (B), or in said at least one composition (A) and said at
least one composition (B).
71. A composition according to claim 70, wherein said at least one
thickening agent is present in an amount ranging from 0.01% to 10% by
weight relative to the total weight of the composition.
72. A method for oxidation dyeing keratin fibers comprising: (a) applying
to said keratin fibers at least one composition (A) comprising, in a
dyeing medium: at least one oxidation dye, at least one thickening
polymer comprising at least one fatty chain, and at least one fatty
alcohol comprising more than twenty carbon atoms; and (b) developing the
color with the aid of at least one oxidizing composition (B) comprising
at least one oxidizing agent, wherein said at least one oxidizing
composition (B) is combined at the time of use with said at least one
composition (A) or said at least one oxidizing composition (B) is applied
sequentially to said at least one composition (A) without intermediate
rinsing.
73. A method according to claim 72, wherein said keratin fibers are chosen
from human keratin fibers.
74. A method according to claim 73, wherein said human keratin fibers are
human hair.
75. A method for oxidation dyeing keratin fibers comprising: applying to
said keratin fibers at least one cosmetic dyeing composition comprising,
in a dyeing medium, at least one oxidation dye and at least one fatty
alcohol comprising more than twenty carbon atoms, and optionally
comprising at least one thickening polymer comprising at least one fatty
chain, developing the color with the aid of at least one oxidizing
composition comprising at least one oxidizing agent and an effective
quantity of at least one thickening polymer comprising at least one fatty
chain, wherein said at least one oxidizing composition is combined at the
time of use with said at least one dyeing composition or wherein said at
least one oxidizing composition is applied sequentially to said at least
one dyeing composition without intermediate rinsing.
76. A method according to claim 75, wherein said keratin fibers are chosen
from human keratin fibers.
77. A method according to claim 76, wherein said human keratin fibers are
human hair.
78. A kit for dyeing keratin fibers comprising at least two compartments
wherein: a first compartment comprises (1) at least one oxidation dye,
(2) at least one thickening polymer comprising at least one fatty chain,
and (3) at least one fatty alcohol comprising more than twenty carbon
atoms, and a second compartment comprises at least one oxidizing agent.
79. A kit according to claim 78, wherein said keratin fibers are chosen
from human keratin fibers.
80. A kit according to claim 79, wherein said human keratin fibers are
human hair.
81. A kit for dyeing keratin fibers comprising at least two compartments
wherein: a first compartment comprises at least one oxidation dye and at
least one fatty alcohol comprising more than twenty carbon atoms, and
optionally comprises at least one thickening polymer comprising at least
one fatty chain and a second compartment comprises at least one oxidizing
agent and an effective quantity of at least one thickening polymer
comprising at least one fatty chain.
82. A kit according to claim 81, wherein said keratin fibers are chosen
from human keratin fibers.
83. A kit according to claim 82, wherein said human keratin fibers are
human hair.
84. A kit for dyeing keratin fibers comprising at least three compartments
wherein: a first compartment comprises at least one oxidation dye and at
least one fatty alcohol comprising more than twenty carbon atoms, and
optionally comprises at least one thickening polymer comprising at least
one fatty chain, a second compartment comprises at least one thickening
polymer comprising at least one fatty chain and a third compartment
comprises at least one oxidizing agent and optionally comprises at least
one thickening polymer comprising at least one fatty chain.
85. A kit according to claim 84, wherein said keratin fibers are chosen
from human keratin fibers.
86. A kit according to claim 85, wherein said human keratin fibers are
human hair.
87. A composition according to claim 10, wherein said anionic thickening
polymers are chosen from copolymers formed from at least three monomers,
wherein at least one of said at least three monomers is chosen from a
carboxylic acid with .alpha.,.beta.-monoethylenic unsaturation, at least
one of said at least three monomers is chosen from an ester of a
carboxylic acid with .alpha.,.beta.-monoethylenic unsaturation, and at
least one of said at least three monomers is chosen from an
oxyalkylenated fatty alcohol.
88. A composition according to claim 23, wherein said hydrophilic
sequences are chosen from hydrophilic sequences of a polyoxyethylenated
nature and wherein said hydrophobic sequences are chains chosen from
aliphatic chains, cycloaliphatic chains, and aromatic chains.
89. A composition according to claim 49, wherein said at least one fatty
alcohol comprising at most twenty carbon atoms is chosen from linear and
branched, saturated and unsaturated fatty alcohols comprising at most
twenty carbon atoms.
Description
[0001] The present invention relates to cosmetic compositions for
oxidation dyeing keratin fibers, such as human keratin fibers like hair,
comprising, in a dyeing medium, (1) at least one oxidation dye, (2) at
least one thickening polymer comprising at least one fatty chain, and (3)
at least one fatty alcohol comprising more than twenty carbon atoms.
[0002] It is known to dye keratin fibers, for example human hair, with
dyeing compositions comprising oxidation dye precursors, generally called
"oxidation bases." Representative oxidation bases include ortho- and
para-phenylenediamines, ortho- and para-aminophenols, and heterocyclic
bases.
[0003] Oxidation dye precursors are compounds initially only slightly
colored or not colored that develop their dyeing power in the hair in the
presence of oxidizing agents, leading to the formation of colored
compounds. The formation of these colored compounds results either from
oxidative condensation of the "oxidation bases" with themselves, or
oxidative condensation of the "oxidation bases" with color-modifying
compounds, or "couplers," which are generally present in the dyeing
compositions used in oxidation dyeing. Representative couplers include
meta-phenylenediamines, meta-aminophenols, meta-diphenols, and certain
heterocyclic compounds.
[0004] The variety of compositions that can be employed in oxidation
coloration, chosen from oxidation bases, oxidation couplers and mixtures
of oxidation bases and couplers, can contribute to a pallet very rich in
color.
[0005] Traditional thickeners, which can provide a gelling effect when
diluted by water and/or surfactants, have been used conventionally to
localize the dye product as applied on hair, so that the dye product does
not touch the face or the area outside the area to be dyed. Such
thickeners, chosen as appropriate, for example include crosslinked
polyacrylic acid, hydroxyethylcelluloses, certain polyurethanes, waxes or
mixtures of nonionic surfactants having an HLB (Hydrophilic Lipophilic
Balance).
[0006] However, the inventors have observed that the above-mentioned
thickening systems may impede a result of intense and chromatic shades of
low selectivity and good fastness and a good cosmetic condition to the
treated hair. However, it has also been observed that the ready-to-use
dyeing compositions comprising known oxidation dye(s) and thickening
systems tend to result in imprecise application of such compositions
and/or a decrease in viscosity over time.
[0007] The inventors have discovered that it is possible to obtain
ready-to-use oxidation dyeing compositions that resist running and tend
to remain well-confined to the site of application. Additionally, such
compositions may favor more intense and more chromatic (radiant) shades,
while exhibiting low selectivities and good fastness toward chemical
agents (shampoo, permanent waving and the like) and/or natural agents
(light, perspiration and the like), and while offering the hair good
cosmetic properties. The inventors have discovered that it is possible to
obtain at least one of the aforementioned characteristics by formulating
a ready-to-use cosmetic dyeing composition comprising (1) at least one
oxidation dye, (2) at least one thickening polymer comprising at least
one fatty chain, and (3) at least one fatty alcohol comprising more than
twenty carbon atoms.
[0008] The inventors have also discovered that said cosmetic compositions
comprising (1) at least one oxidation dye, (2) at least one thickening
polymer comprising at least one fatty chain, and (3) at least one fatty
alcohol comprising more than twenty carbon atoms tend to be stable upon
storage.
[0009] At least one of these discoveries forms the basis of the present
invention.
[0010] The subject of the present invention is thus a cosmetic composition
for oxidation dyeing keratin fibers, such as human keratin fibers like
hair, comprising, in a dyeing medium (1) at least one oxidation dye, (2)
at least one thickening polymer comprising at least one fatty chain, and
(3) at least one fatty alcohol comprising more than twenty carbon atoms.
[0011] Another subject of the invention relates to a ready-to-use cosmetic
composition for oxidation dyeing keratin fibers comprising, in a dyeing
medium, (1) at least one oxidation dye, (2) at least one thickening
polymer comprising at least one fatty chain, (3) at least one fatty
alcohol comprising more than twenty carbon atoms, and (4) at least one
oxidizing agent. The term "ready-to-use composition" is understood to
mean, for the purposes of the present invention, a composition intended
to be applied immediately to the keratin fibers, either stored as it is
before use or obtained from the mixture of two or more compositions.
[0012] The invention also relates to a method for oxidation dyeing keratin
fibers, such as human keratin fibers like hair, comprising applying to
said keratin fibers at least one composition (A) comprising, in a dyeing
medium:
[0013] at least one oxidation dye,
[0014] at least one thickening polymer comprising at least one fatty
chain, and
[0015] at least one fatty alcohol comprising more than twenty carbon
atoms, developing the color with the aid of at least one composition (B)
comprising at least one oxidizing agent, wherein said at least one
oxidizing composition (B) is combined at the time of use with said at
least one composition (A) or said at least one oxidizing composition (B)
is applied sequentially to said at least one composition (A) without
intermediate rinsing.
[0016] A variation of the above-described method is a method for oxidation
dyeing keratin fibers, such as human keratin fibers like hair,
comprising:
[0017] applying to said keratin fibers at least one dyeing composition
comprising, in a dyeing medium, at least one oxidation dye and at least
one fatty alcohol comprising more than twenty carbon atoms, and
optionally comprising at least one thickening polymer comprising at least
one fatty chain,
[0018] developing the color with the aid of at least one oxidizing
composition comprising at least one oxidizing agent and an effective
quantity of at least one thickening polymer comprising at least one fatty
chain,
[0019] wherein said at least one oxidizing composition is combined at the
time of use with said at least one dyeing composition or wherein said at
least one oxidizing composition is applied sequentially to said at least
one dyeing composition without intermediate rinsing.
[0020] One embodiment of the invention relates to multicompartment dyeing
devices or "kits" for oxidation dyeing keratin fibers, such as human
keratin fibers like hair.
[0021] A kit according to the invention comprises at least two
compartments, wherein:
[0022] a first compartment comprises (1) at least one oxidation dye, (2)
at least one thickening polymer comprising at least one fatty chain, and
(3) at least one fatty alcohol comprising more than twenty carbon atoms,
and
[0023] a second compartment comprises at least one oxidizing agent.
[0024] According to one variant, another kit comprises at least two
compartments, wherein:
[0025] a first compartment comprises at least one oxidation dye and at
least one fatty alcohol comprising more than twenty carbon atoms, and
optionally comprises at least one thickening polymer comprising at least
one fatty chain and
[0026] a second compartment comprises at least one oxidizing agent and an
effective quantity of at least one thickening polymer comprising at least
one fatty chain.
[0027] According to another variant, a three-compartment kit comprises:
[0028] a first compartment comprising at least one oxidation dye and at
least one fatty alcohol comprising more than twenty carbon atoms, and
optionally comprising at least one thickening polymer comprising at least
one fatty chain,
[0029] a second compartment comprising at least one thickening polymer
comprising at least one fatty chain and
[0030] a third compartment comprising at least one oxidizing agent and
optionally comprising at least one thickening polymer comprising at least
one fatty chain.
[0031] At least one fatty alcohol comprising more than 20 carbon atoms
[0032] The expression fatty alcohols includes, but is not limited to,
fatty alcohols chosen from branched and unbranched, saturated and
unsaturated fatty alcohols. The expression at least one (as used herein,
"at least one" means one or more and thus includes mixtures and
combinations) fatty alcohol comprising more than 20 carbon atoms
includes, but is not limited to, fatty alcohols comprising more than
twenty carbon atoms, mixtures of fatty alcohols comprising at least 30%
by weight of at least one fatty alcohol comprising more than twenty
carbon atoms, and mixtures of fatty alcohols comprising more than 30% by
weight of at least one fatty alcohol comprising more than twenty carbon
atoms. In one embodiment the fatty alcohol is a pure alcohol, i.e., a
single fatty alcohol comprising more than 20 carbon atoms.
[0033] Representative at least one fatty alcohol that can be used
according to the invention include for example behenyl alcohol and erucyl
alcohol.
[0034] There may also be mentioned the commercial products NAFOL 18-22,
NAFOL 18-22B, NAFOL 18-22 C, NAFOL 20+, NAFOL 20-22, and NACOL 22-98 from
the company CONDEA, the commercial product CRODACID PG 3220 from the
company CRODA, and the commercial product EDENOR U 122 from the company
HENKEL.
[0035] The at least one fatty alcohol comprising more than twenty carbon
atoms may be present in an amount ranging for example from 0.01% to 30%
by weight relative to the total weight of the composition, such as from
0.05% to 20% by weight relative to the total weight of the composition,
and further such as from 0.1% to 15% by weight relative to the total
weight of the composition.
[0036] At least one thickening polymer comprising at least one fatty chain
[0037] The at least one thickening polymer comprising at least one fatty
chain according to the invention can be chosen from nonionic, anionic and
cationic thickening polymers comprising at least one fatty chain.
[0038] (i) Anionic Thickeners
[0039] Such anionic thickening polymers comprising at least one fatty
chain can be chosen from:
[0040] (I) anionic polymers comprising at least one hydrophilic unit and
at least one allyl ether unit comprising at least one fatty chain, for
example said anionic polymers wherein said at least one hydrophilic unit
comprises at least one ethylenic unsaturated anionic monomeric residue,
such as vinylcarboxylic acid and further such as at least one monomeric
residue chosen from acrylic acid and methacrylic acid residues, and
wherein said at least one allyl ether unit comprising at least one fatty
chain corresponds to the monomeric residue resulting from the monomer of
formula (I):
CH.sub.2.dbd.C--R'--CH.sub.2--O--B.sub.n--R (I)
[0041] in which R' is chosen from H and CH.sub.3, B is chosen from
ethyleneoxy groups, n is chosen from zero and integers ranging from 1 to
100, R is a hydrocarbon group chosen from alkyl, arylalkyl, aryl,
alkylaryl and cycloalkyl groups, comprising from 8 to 30 carbon atoms,
such as from 10 to 24, and further such as from 12 to 18 carbon atoms.
One embodiment of the invention comprises at least one allyl ether unit
of the monomeric resudue resulting from the monomer of formula (I),
wherein R' is H, n is equal to 10, and R is a stearyl (C.sub.18) group.
[0042] Representative anionic amphiphilic polymers of this type are
described and prepared, according to a method of emulsion polymerization,
in patent EP-0,216,479, the disclosure of which is incorporated by
reference herein.
[0043] As used herein, the term "lower alkyl" means an alkyl chosen from
saturated and unsaturated, branched and unbranched C.sub.1-C.sub.6 alkyl
groups.
[0044] Representative anionic thickening polymers comprising at least one
fatty chain include for example polymers formed from 20% to 60% by weight
of at least one monomer chosen from acrylic acid and methacrylic acid, 5%
to 60% by weight of C.sub.1-C.sub.6 alkyl(meth)acrylates, 2% to 50% by
weight of allyl ether comprising at least one fatty chain of formula (I),
and up to 1% by weight of a crosslinking agent chosen from well known
copolymerizable polyethylenic unsaturated monomers such as diallyl
phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol
dimethacrylate and methylenebisacrylamide.
[0045] One embodiment could comprise at least one anionic thickening
polymer chosen from crosslinked terpolymers of methacrylic acid, ethyl
acrylate, and polyethylene glycol (10 EO) stearyl alcohol ether (Steareth
10), such as the products sold by the company ALLIED COLLOIDS under the
names SALCARE SC 80 and SALCARE SC 90, which are aqueous emulsions
comprising 30% of a crosslinked terpolymer of methacrylic acid, of ethyl
acrylate and of steareth-10-allyl ether (40/50/10).
[0046] Anionic thickening polymers comprising at least one fatty chain can
also be chosen from:
[0047] (II) anionic polymers comprising at least one hydrophilic unit of
the olefinic unsaturated carboxylic acid type and at least one
hydrophobic unit of the (C.sub.10-C.sub.30)alkyl ester of unsaturated
carboxylic acid type.
[0048] Such polymers are chosen from polymers comprising:
[0049] at least one hydrophilic unit formed from olefinic unsaturated
carboxylic acid monomers of formula (II): 1
[0050] in which R.sub.1 is chosen from H, CH.sub.3, and C.sub.2H.sub.5,
(which corresponds with acrylic acid, methacrylic acid and ethacrylic
acid units), and
[0051] at least one hydrophobic unit formed from (C.sub.10-C.sub.30)alkyl
esters of unsaturated carboxylic acid monomers of formula (III): 2
[0052] in which R.sub.2 is chosen from H, CH.sub.3, and C.sub.2H.sub.5,
(which corresponds with acrylate, methacrylate and ethacrylate units) and
R.sub.3 is chosen from saturated and unsaturated, branched and unbranched
C.sub.10-C.sub.30 alkyl groups. In one embodiment, for example, R.sub.2
is chosen from H (acrylate units) and CH.sub.3 (methacrylate units) and
R.sub.3 is chosen from C.sub.12-C.sub.22 alkyl groups.
[0053] (C.sub.10-C.sub.30)alkyl esters of unsaturated carboxylic acids in
accordance with the invention include for example lauryl acrylate,
stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate,
lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl
methacrylate, and dodecyl methacrylate.
[0054] Anionic polymers of this type are for example described and
prepared according to U.S. Pat. Nos. 3,915,921 and 4,509,949, the
disclosures of which are incorporated by reference herein.
[0055] Anionic thickening polymers comprising at least one fatty chain
that can be used include polymers formed from a mixture of monomers
comprising:
[0056] (i) acrylic acid,
[0057] (ii) at least one ester of formula (III) described above wherein
R.sub.2 is chosen from H and CH.sub.3, and R.sub.3 is chosen from alkyl
groups comprising from 12 to 22 carbon atoms, and
[0058] (iii) at least one crosslinking agent chosen from well known
copolymerizable polyethylenic unsaturated monomers such as diallyl
phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol
dimethacrylate and methylenebisacrylamide.
[0059] Representative anionic thickening polymers comprising at least one
fatty chain that can be used include (i) polymers comprising 95% to 60%
by weight of acrylic acid monomeric residue (hydrophilic unit), 4% to 40%
by weight of C.sub.10-C.sub.30 alkyl acrylate monomeric residue
(hydrophobic unit), and 0% to 6% by weight of crosslinking polymerizable
monomeric residue, and (ii) polymers comprising 98% to 96% by weight of
acrylic acid monomeric residue (hydrophilic unit), 1% to 4% by weight of
C.sub.10-C.sub.30 alkyl acrylate monomeric residue (hydrophobic unit) and
0.1% to 0.6% by weight of crosslinking polymerizable monomeric residue
such as those described above.
[0060] Among the above polymers, the products sold by the company GOODRICH
under the trade names PEMULEN TR1, PEMULEN TR2, and CARBOPOL 1382 can be
used. One embodiment could employ at least one polymer chosen from
PEMULEN TR1, and the product sold by the company S.E.P.P.I.C. under the
name COATEX SX.
[0061] Anionic thickening polymers comprising at least one fatty chain can
also be chosen from:
[0062] (III) terpolymers formed from maleic anhydride/C.sub.30-C.sub.38
.alpha.-olefin/alkyl maleate such as the product (maleic
anhydride/C.sub.30-C.sub.38 .alpha.-olefin/isopropyl maleate copolymer)
sold under the name PERFORMA V 1608 by the company NEWPHASE TECHNOLOGIES,
[0063] (IV) acrylic terpolymers formed from:
[0064] (a) 20% to 70% by weight of a carboxylic acid with
.alpha.,.beta.-monoethylenic unsaturation
[0065] (b) 20% to 80% by weight of a nonsurfactant monomer with
.alpha.,.beta.-monoethylenic unsaturation different from (a)
[0066] (c) 0.5% to 60% by weight of a nonionic monourethane which is the
product of the reaction of a monohydric surfactant with a monoisocyanate
with monoethylenic unsaturation
[0067] such as acrylic terpolymers described in patent application
EP-A-0,173,109, the disclosure of which is incorporated by reference
herein, and more particularly acrylic terpolymers described therein in
Example 3, namely a methacrylic acid/methyl acrylate/dimethyl
metaisopropenyl benzyl isocyanate of ethoxylated (40 EO) behenyl alcohol
terpolymer in 25% aqueous dispersion,
[0068] (V) copolymers formed from at least two monomers, wherein at least
one of said at least two monomers is chosen from a carboxylic acid with
.alpha.,.beta.-monoethylenic unsaturation, an ester of a carboxylic acid
with .alpha.,.beta.-monoethylenic unsaturation, and an oxyalkylenated
fatty alcohol, and
[0069] (VI) copolymers formed from at least three monomers, wherein at
least one of said at least three monomers is chosen from a carboxylic
acid with .alpha.,.beta.-monoethylenic unsaturation, at least one of said
at least three monomers is chosen from an ester of a carboxylic acid with
.alpha.,.beta.-monoethylenic unsaturation and at least one of said at
least three monomers is chosen from an oxyalkylenated fatty alcohol.
[0070] Additionally, these compounds can also comprise, as monomer, a
carboxylic acid ester comprising an .alpha.,.beta.-monoethylenic
unsaturation and a C.sub.1-C.sub.4 alcohol. By way of example of this
type of compound, there may be mentioned ACULYN 22 sold by the company
ROHM and HAAS, which is an oxyalkylenated stearyl methacrylate/ethyl
acrylate/methacrylic acid terpolymer.
[0071] (ii) Nonionic Thickeners
[0072] Nonionic thickening polymers comprising at least one fatty chain
according to the invention can be chosen from:
[0073] (1) celluloses modified by at least one group comprising at least
one fatty chain such as:
[0074] hydroxyethylcelluloses modified by at least one group comprising at
least one fatty chain such as alkyl, arylalkyl and alkylaryl groups and
further such as alkyl, arylalkyl and alkylaryl groups wherein said alkyl
groups comprise from 8-22 carbon atoms, such as the product NATROSOL PLUS
GRADE 330 CS (C.sub.16 alkyls) sold by the company AQUALON, and the
product BERMOCOLL EHM 100 sold by the company BEROL NOBEL,
[0075] hydroxyethylcelluloses modified by at least one polyalkylene glycol
ether of alkylphenol group, such as the product AMERCELL POLYMER HM-1500
(polyethylene glycol (15) ether of nonylphenol) sold by the company
AMERCHOL;
[0076] (2) hydroxypropylguars modified by at least one group comprising at
least one fatty chain such as the product ESAFLOR HM 22 (C.sub.22 alkyl
chain) sold by the company LAMBERTI, the products RE 210-18 (C.sub.14
alkyl chain) and RE 205-1 (C.sub.20 alkyl chain) sold by the company
RHONE POULENC (Succeeded by RHODIA CHIMIE);
[0077] (3) copolymers formed from vinylpyrrolidone and at least one
hydrophobic monomer comprising at least one fatty chain such as for
example:
[0078] the products ANTARON V216 and GANEX V216 (vinylpyrrolidone/hexadece-
ne copolymer) sold by the company I.S.P., and
[0079] the products ANTARON V220 and GANEX V220 (vinylpyrrolidone/eicosene
copolymer) sold by the company I.S.P.;
[0080] (4) copolymers formed from at least one C.sub.1-C.sub.6 alkyl
methacrylate and at least one amphiphilic monomer comprising at least one
fatty chain and copolymers formed from at least one C.sub.1-C.sub.6 alkyl
acrylate and at least one amphiphilic monomer comprising at least one
fatty chain such as for example the oxyethylenated stearyl
acrylate/methyl acrylate copolymer sold by the company GOLDSCHMIDT under
the name ANTIL 208;
[0081] (5) copolymers formed from at least one hydrophilic methacrylate
and at least one hydrophobic monomer comprising at least one fatty chain
and copolymers formed from at least one hydrophilic acrylate and at least
one hydrophobic monomer comprising at least one fatty chain such as for
example the polyethylene glycol methacrylate/lauryl methacrylate
copolymer;
[0082] (6) polyether-polyurethanes comprising in their chain both
hydrophilic sequences which are most often of a polyoxyethylenated nature
and hydrophobic sequences which may be chains chosen from aliphatic
chains, cycloaliphatic chains, and aromatic chains;
[0083] (7) polymers comprising an aminoplast ether backbone possessing at
least one fatty chain, such as the compounds PURE THIX provided by the
company SUD-CHEMIE.
[0084] Nonionic thickening polymers can additionally include
polyether-polyurethanes comprising at least two lipophilic (i.e.,
hydrophobic) hydrocarbon chains, comprising from 6 to 30 carbon atoms,
separated by a hydrophilic sequence, it being possible for the
hydrocarbon chains to be chosen from pendant chains and chains at the end
of a hydrophilic sequence. One embodiment may comprise at least one
pendant chain. In addition, the polymer may comprise a hydrocarbon chain
at at least one end of a hydrophilic sequence.
[0085] Representative polyether-polyurethanes useful in the present
invention may be polyblocks, such as in triblock form. The hydrophobic
sequences may be at each end of the chain (for example: triblock
copolymer with hydrophilic central sequence) and optionally both at the
ends and in the chain (polyblock copolymer for example). These same
polymers may also be in the form of graft units or may be star-shaped.
[0086] The nonionic polyether-polyurethanes comprising at least one fatty
chain may be triblock copolymers whose hydrophilic sequence is a
polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated
groups. Certain nonionic polyether-polyurethanes comprise a urethane bond
between the hydrophilic sequences.
[0087] By extension, those whose hydrophilic sequences are linked by other
chemical bonds to the lipophilic sequences are also included among the
nonionic polyether-polyurethanes comprising at least one fatty chain.
[0088] Representative nonionic polyether-polyurethanes comprising at least
one fatty chain include Rholate 205 comprising a urea function sold by
the company RHEOX and Rholate 208, 204 and 212, as well as Acrysol RM
184, Aculyn 44 and Aculyn 46 from the company ROHM and HAAS [ACULYN 46 is
a polycondensate of polyethylene glycol comprising 150 or 180 mol of
ethylene oxide, stearyl alcohol and methylene-bis(4-cyclohexylisocyanate)
(SMDI), at 15% by weight in a maltodextrin (4%) and water (81%) matrix;
ACULYN 44 is a polycondensate of polyethylene glycol comprising 150 or
180 mol of ethylene oxide, decyl alcohol and methylenebis(4-cyclohexyliso-
cyanate) (SMDI), at 35% by weight in a propylene glycol (39%) and water
(26%) mixture].
[0089] There may also be mentioned the product ELFACOS T210 comprising a
C.sub.12-C.sub.14 alkyl chain and the product ELFACOS T212 comprising a
C.sub.18 alkyl chain from AKZO.
[0090] The product DW 1206B from RHOM & HAAS comprising a C.sub.20 alkyl
chain and with a urethane bond, sold at 20% dry matter content in water,
may also be used.
[0091] It is also possible to use solutions and dispersions of these
polymers for example in water and for example in an aqueous-alcoholic
medium. By way of example of such polymers, there may be mentioned
Rholate 255, Rholate 278 and Rholate 244 sold by the company RHEOX. It is
also possible to use the product DW 1206F and DW 1206J provided by the
company ROHM & HAAS.
[0092] Representative polyether-polyurethanes that can be used according
to the invention include polyether-polyurethanes described in the article
by G. Fonnum, J. Bakke and Fk. Hansen--Colloid Polym. Sci 271, 380, 389
(1993), the disclosure of which is incorporated by reference herein.
[0093] (iii) Cationic Thickeners
[0094] As used herein, "cationic thickener" refers to polymers chosen from
polymers comprising at least one cationic group and polymers comprising
at least one group which can be ionized to form cationic groups.
[0095] Representative cationic thickening polymers comprising at least one
fatty chain used in the present invention can be chosen from quaternized
cellulose derivatives and polyacrylates with noncyclic amine-containing
side groups.
[0096] Such quaternized cellulose derivatives can be chosen from:
[0097] quaternized celluloses modified by groups comprising at least one
fatty chain, such as at least one group chosen from alkyl, arylalkyl and
alkylaryl groups comprising at least 8 carbon atoms,
[0098] quaternized hydroxyethylcelluloses modified by at least one group
comprising at least one fatty chain, such as at least one group chosen
from alkyl, arylalkyl and alkylaryl groups comprising at least 8 carbon
atoms.
[0099] In one embodiment, said alkyl groups carried by the above
quaternized celluloses and hydroxyethylcelluloses comprise from 8 to 30
carbon atoms and the aryl groups are chosen from phenyl, benzyl, naphthyl
and anthryl groups.
[0100] There may be mentioned as examples of quaternized
alkylhydroxyethylcelluloses comprising at least one C.sub.8-C.sub.30
fatty chain the products QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A,
QUATRISOFT LM-X 529-18B (C.sub.12 alkyl) and QUATRISOFT LM-X 529-8
(C.sub.18 alkyl) marketed by the company AMERCHOL and the products
CRODACEL QM, CRODACEL QL (C.sub.12 alkyl) and CRODACEL QS (C.sub.18
alkyl) marketed by the company CRODA.
[0101] Representative polyacrylates with amine-containing side groups,
quaternized and otherwise, comprise for example hydrophobic groups of the
steareth 20 type (polyoxyethylenated stearyl alcohol (20)).
[0102] As examples of polyacrylates with amine-containing side groups,
there may be mentioned the polymers 8781-121B or 9492-103 from the
company NATIONAL STARCH.
[0103] One embodiment of the oxidation dyeing composition according to the
invention may comprise at least one nonionic thickening polymer
comprising at least one fatty chain.
[0104] The anionic, nonionic and cationic at least one thickening polymer
comprising at least one fatty chain is generally present in an amount
ranging for example from 0.01% to 10% by weight relative to the total
weight of the dyeing composition, such as from 0.1% to 5% by weight
relative to the total weight of the dyeing composition.
[0105] Oxidation dyes
[0106] The at least one oxidation dye which can be used according to the
present invention is chosen from oxidation bases, and oxidation couplers.
In one embodiment, the compositions can comprise at least one oxidation
base.
[0107] The oxidation bases usable in the context of the present invention
are chosen from those conventionally known as oxidation dyes.
Representative oxidation dyes include ortho- and para-phenylenediamines,
double bases, ortho- and para-aminophenols and heterocyclic bases as well
as their addition salts with an acid.
[0108] For example, the following oxidation bases may be used:
[0109] (I) para-phenylenediamines chosen from compounds of formula (I),
and their acid addition salts: 3
[0110] wherein:
[0111] R.sub.1 is chosen from hydrogen, C.sub.1-C.sub.4 alkyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, polyhydroxy(C.sub.2-C.sub.4
alkyl) groups, (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups,
phenyl groups, 4'-aminophenyl groups, and C.sub.1-C.sub.4 alkyl groups
substituted with at least one group chosen from nitrogen-containing
groups,
[0112] R.sub.2 is chosen from hydrogen, C.sub.1-C.sub.4 alkyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, polyhydroxy(C.sub.2-C.sub.4
alkyl) groups, (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups, and
C.sub.1-C.sub.4 alkyl groups substituted with a nitrogen-containing
group;
[0113] R.sub.1 and R.sub.2 may also form, together with the nitrogen atom
to which they are bonded, a 5- or 6-membered nitrogen-containing
heterocycle ring, optionally substituted with at least one group chosen
from alkyl groups, hydroxyl groups and ureido groups;
[0114] R.sub.3 is chosen from hydrogen, halogens, such as chlorine,
C.sub.1-C.sub.4 alkyl groups, sulfo groups, carboxyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, hydroxy(C.sub.1-C.sub.4
alkyoxy) groups, acetylamino(C.sub.1-C.sub.4 alkoxy) groups,
mesylamino(C.sub.1-C.sub.4 alkoxy) groups, and carbamoylamino(C.sub.1-C.s-
ub.4 alkoxy) groups;
[0115] R.sub.4 is chosen from hydrogen, halogens, and C.sub.1-C.sub.4
alkyl groups.
[0116] Suitable nitrogen-containing groups of formula (I) above may, for
example, be chosen from amino,(C.sub.1-C.sub.4) monoalkylamino,
(C.sub.1-C.sub.4)dialkylamino, (C.sub.1-C.sub.4)trialkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium, and ammonium
groups.
[0117] Representative para-phenylenediamines of formula (I) above which
may be used include para-phenylenediamine, para-tolylenediamine,
2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline, N,N-bis(.beta.-hydroxyethyl)-para-ph-
enylenediamine, 4-N,N-bis(.beta.-hydroxyethyl)amino-2-methylaniline,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-chloroaniline,
2-.beta.-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediami-
ne, 2-isopropyl-para-phenylenediamine, N-(.beta.-hydroxypropyl)-para-pheny-
lenediamine, 2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-.beta.-hydroxyeth-
yl)-para-phenylenediamine, N-(.beta.,.gamma.-dihydroxypropyl)-para-phenyle-
nediamine, N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine, 2-.beta.-hydroxyethyloxy-para-phenylenedi-
amine, 2-.beta.-acetylaminoethyloxy-para-phenylenediamine,
N-(.beta.-methoxyethyl)-para-phenylenediamine, 2-methyl-1-N-.beta.-hydrox-
yethyl-para-phenylenediamine and their acid addition salts.
[0118] In other embodiments of the present invention,
para-phenylenediamines of formula (I) above can, for example, be chosen
from para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenyl-
enediamine, 2-.beta.-hydroxyethyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenyle-
nediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylened-
iamine, N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
2-chloro-para-phenylenediamine, and their acid addition salts.
[0119] According to the invention, "double bases" is understood to mean
the compounds comprising at least two aromatic rings on which at least
one functional group chosen from amino groups and hydroxyl groups are
carried.
[0120] (II) double bases chosen from compounds comprising at least two
aromatic rings substituted with at least one group chosen from amino and
hydroxyl groups. Such double bases may be chosen from compounds of
formula (II), and their acid addition salts: 4
[0121] wherein:
[0122] Z.sub.1 and Z.sub.2, which may be identical or different, are each
chosen from hydroxyl groups, and --NH.sub.2 groups, optionally
substituted with a group chosen from C.sub.1-C.sub.4 alkyl groups, and
linkers Y;
[0123] linker Y is chosen from linear and branched, divalent alkylene
groups comprising from 1 to 14 carbon atoms, optionally interrupted by,
or optionally terminating with, at least one entity chosen from
nitrogen-containing groups and heteroatoms such as oxygen, sulfur, and
nitrogen, and optionally substituted with at least one group chosen from
hydroxyl groups, and C.sub.1-C.sub.6 alkoxy groups;
[0124] R.sub.5 and R.sub.6, which may be identical or different, are each
chosen from hydrogen, halogens, C.sub.1-C.sub.4 alkyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, polyhydroxy(C.sub.2-C.sub.4
alkyl) groups, amino(C.sub.1-C.sub.4 alkyl) groups, and linkers Y;
[0125] R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12, which
may be identical or different, are each chosen from hydrogen, linkers Y,
and C.sub.1-C.sub.4 alkyl groups;
[0126] provided that said compounds of formula (II) comprise only one
linker Y per molecule.
[0127] Suitable nitrogen-containing groups of formula (II) include
mono(C.sub.1-C.sub.4)alkylamino, (C.sub.1-C.sub.4)dialkylamino,
(C.sub.1-C.sub.4)trialkylamino, monohydroxy(C.sub.1-C.sub.4)alkylamino,
imidazolinium and ammonium groups.
[0128] Representative double bases of formula (II) include
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropano-
l, N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(.beta.-hydroxyethy-
l)-N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4-methylaminophe-
nyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphen-
yl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their
acid addition salts.
[0129] In another embodiment of the invention, the double bases of formula
(II) may be chosen from N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminoph-
enyl)-1,3-diaminopropanol, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane,
and their acid addition salts.
[0130] (III) para-aminophenols chosen from compounds of formula (III), and
their acid addition salts: 5
[0131] wherein:
[0132] R.sub.13 is chosen from hydrogen, halogens, such as fluorine,
C.sub.1-C.sub.4 alkyl groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups,
amino(C.sub.1-C.sub.4 alkyl), and hydroxy(C.sub.1-C.sub.4)alkylamino(C.su-
b.1-C.sub.4 alkyl) groups;
[0133] R.sub.14 is chosen from hydrogen, halogens, such as fluorine,
C.sub.1-C.sub.4 alkyl groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
polyhydroxy(C.sub.2-C.sub.4 alkyl) groups, amino(C.sub.1-C.sub.4 alkyl)
groups, cyano(C.sub.1-C.sub.4 alkyl) groups, and (C.sub.1-C.sub.4)alkoxy(-
C.sub.1-C.sub.4)alkyl groups.
[0134] Representative para-aminophenols of formula (III) above include
para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,
4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,
4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol,
4-amino-2-aminomethylphenol, 4-amino-2-(.beta.-hydroxyethylaminomethyl)ph-
enol, and their acid addition salts.
[0135] (IV) ortho-aminophenols chosen, for example, from 2-aminophenol,
2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6-methylbenzene,
5-acetamido-2-aminophenol, and their acid addition salts.
[0136] (V) heterocyclic bases chosen, for example, from pyridine
derivatives, pyrimidine derivatives, pyrazole derivatives,
pyrazolo-pyrimidine derivatives, and their acid addition salts.
[0137] Representative pyridine derivatives include 2,5-diaminopyridine,
2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,
2-(.beta.-methoxyethyl)amino-3-amino-6-methoxypyridine,
3,4-diaminopyridine, and their acid addition salts. Some of the
aforementioned pyridine derivatives have been described, for example in
the patents GB 1,026,978 and GB 1,153,196, the disclosures of which are
incorporated by reference herein.
[0138] Representative pyrimidine derivatives include
2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,
2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine,
2,5,6-triaminopyrimidine, and their acid addition salts. Some of the
aforementioned pyrimidine derivatives have been described, for example in
German Patent DE 2,359,399, Japanese Patents JP 88-169,571 and JP
91-10659, and Patent Application WO 96/15765, the disclosures of which
are incorporated by reference herein.
[0139] Representative pyrazolo-pyrimidine derivatives include those
described, for example, in the patent application FR-A-2 750 048, the
disclosure of which is incorporated by reference herein. Such
pyrazolo-pyrimidine derivatives include pyrazolo[1,5-a]pyrimidines, such
as
[0140] pyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0141] 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0142] pyrazolo[1,5-a]pyrimidine-3,5-diamine;
[0143] 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;
[0144] 3-aminopyrazolo[1,5-a]pyrimidin-7-ol;
[0145] 3-aminopyrazolo[1,5-a]pyrimidin-5-ol;
[0146] 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;
[0147] 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;
[0148] 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)amino]eth-
anol;
[0149] 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]eth-
anol;
[0150] 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0151] 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0152] 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0153] 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine;
their salts, such as their acid addition salts, and their tautomeric
forms when a tautomeric equilibrium exists.
[0154] Representative pyrazole derivatives include 4,5-diamino-1-methylpyr-
azole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole,
4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,
4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopy-
razole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1--
methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)pyrazole, 4,5-diamino-1-ethyl-3-methyl-
pyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl--
1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino--
1,3-dimethylpyrazole, 3,4,5-triaminopyrazole,1-methyl-3,4,5-triaminopyrazo-
le, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(.beta.-hydr-
oxyethyl)amino-1-methylpyrazole, and their acid addition salts. Some of
the aforementioned pyrazole derivatives have been described, for example
in Patents DE 3,843,892, DE 4,133,957 and Patent Applications WO
94/08969, WO 94/08970, FR-A-2,733,749 and DE 195 43 988, the disclosures
of which are incorporated by reference herein.
[0155] In accordance with the present invention, the oxidation bases are
generally present in an amount ranging for example from 0.0005% to 12% by
weight, relative to the total weight of the composition, such as from
0.005% to 8%.
[0156] Suitable couplers which may be used in the dyeing process of the
invention include couplers conventionally used in oxidation dyeing
compositions. Such couplers can be chosen, for example, from
meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthols,
sesamol and its derivatives, heterocyclic couplers, such as, for example,
indole derivatives, indoline derivatives, pyridine derivatives,
pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles,
benzothiazoles, benzoxazoles, 1,3-benzodioxoles, quinolines and their
acid addition salts.
[0157] Representative couplers include 2-methyl-5-aminophenol,
5-N-(.beta.-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,
1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,
4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(.beta.-hydroxyethyloxy)benz-
ene, 2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol,
.alpha.-naphthol, 6-hydroxyindole, 4-hydroxyindole,
4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridi-
ne, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,
1-amino-2-methoxy-4,5-methylenedioxybenzene, 2-amino-3-hydroxypyridine,
3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole, 2,6-dimethylpyrazolo[1,5-b]-1-
,2,4-triazole, and their acid addition salts.
[0158] When these couplers are present, they are generally present in an
amount ranging for example from 0.0001% to 10% by weight, relative to the
total weight of the composition, such as from 0.005% to 5%.
[0159] Generally, the acid addition salts of the oxidation bases and
couplers can be chosen from hydrochlorides, hydrobromides, sulfates,
tartrates, lactates and acetates.
[0160] The compositions according to the invention may also comprise at
least one direct dye. Representative direct dyes which can be used in the
present invention include direct dyes that have conventionally been used
in direct dyeing compositions and lighting direct dyeing compositions.
For example, the dyes can be chosen from neutral, cationic, and anionic
nitro dyes, neutral, cationic, and anionic anthraquinone dyes, and
neutral, cationic, and anionic azo dyes. Generally, the direct dyes are
present in amounts ranging for example from 0.001% to 20% by weight of
the total weight of the composition, such as for example from 0.01% to
10% by weight of the total weight of the composition.
[0161] In one embodiment of the invention, namely within the ready-to-use
composition, said at least one composition (A) and said at least one
composition (B) can further comprise at least one polymer chosen from
cationic and amphoteric polymers, such as substantive polymers.
[0162] Cationic polymers
[0163] As used herein, "cationic polymer" refers to polymers chosen from
polymers comprising at least one cationic group and polymers comprising
at least one group which can be ionized to form cationic groups.
[0164] Representative cationic polymers which may be used in accordance
with the present invention include any of those already known to improve
at least one cosmetic property of hair, such as, for example, those
described in patent application EP-A-0 337 354 and in French patent
applications FR-A-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519
863, the disclosures of which are incorporated herein by reference.
[0165] According to the present invention, the at least one cationic
polymer may be chosen from polymers comprising at least one unit, wherein
said at least one unit comprises at least one group chosen from primary
amine groups, secondary amine groups, tertiary amine groups and
quaternary amine groups, wherein said at least one group forms part of
the polymer skeleton, or is carried by at least one lateral substituent
on said polymer skeleton.
[0166] According to the present invention, the at least one cationic
polymer has a number-average molecular mass generally ranging for example
from 500 to 5.times.10.sup.6, such as from 1.times.10.sup.3to
3.times.10.sup.6.
[0167] The at least one cationic polymer may, for example, be chosen from
polymers of quaternary polyammonium type, polymers of polyamino amide
type and polymers of polyamine type. Such types of polymers are known in
the art. They are for example described in French patents Nos. 2, 505,
348 and 2, 542, 997, the disclosures of which are incorporated by
reference herein.
[0168] Non-limiting examples of cationic polymers include:
[0169] (1) homo- and co-polymers derived from at least one monomer chosen
from acrylic esters, methacrylic esters and amides, wherein said homo-
and co-polymers comprise at least one unit chosen from units of formulae:
6
[0170] wherein:
[0171] R.sub.3, which may be identical or different, are each chosen from
hydrogen atoms and CH.sub.3 groups;
[0172] A, which may be identical or different, are each chosen from linear
and branched alkyl groups comprising from 1 to 6 carbon atoms, such as 2
and 3 carbon atoms, and hydroxyalkyl groups comprising from 1 to 4 carbon
atoms;
[0173] R.sub.4, R.sub.5 and R.sub.6, which may be identical or different,
are each chosen from alkyl groups comprising from 1 to 18 carbon atoms,
such as from 1 to 6 carbon atoms, and benzyl groups;
[0174] R.sub.1and R.sub.2, which may be identical or different, are each
chosen from hydrogen atoms and alkyl groups comprising from 1 to 6 carbon
atoms, such as methyl and ethyl;
[0175] X.sup.- is an anion chosen from anions derived from at least one
inorganic acid and anions derived from at least one organic acid, such as
methosulfate anions and halides, such as chlorides and bromides.
[0176] Copolymers of family (1) may further comprise at least one unit
derived from at least one comonomer chosen from vinyllactams, vinyl
esters, acrylamides, methacrylamides, diacetone acrylamides, acrylamides
and methacrylamides substituted on the nitrogen with at least one group
chosen from (C.sub.1-C.sub.4) alkyls, acrylic acids, methacrylic acids,
acrylic esters, and methacrylic esters. Non-limiting examples of
vinyllactams include vinylpyrrolidone and vinylcaprolactam.
[0177] Non-limiting examples of copolymers of family (1) include:
[0178] copolymers derived from at least one monomer of (i) acrylamide and
(ii) dimethylaminoethyl methacrylate quaternized with at least one group
chosen from dimethyl sulfate and dimethyl halide, such as the product
sold under the name HERCOFLOC by the company Hercules;
[0179] copolymers derived from at least one monomer of (i) acrylamide and
(ii) methacryloyloxyethyltrimethylammonium chloride described, for
example, in patent application EP-A-080 976, the disclosure of which is
incorporated herein by reference, and which is sold under the name BINA
QUAT P 100 by the company Ciba Geigy;
[0180] copolymers derived from at least one monomer of (i) acrylamide and
(ii) methacryloyloxyethyltrimethylammonium methosulfate, such as, for
example, copolymers sold under the name RETEN by the company Hercules;
[0181] quaternized and non-quaternized vinylpyrrolidone/dialkylaminoalkyl
acrylate copolymers and quaternized and non-quaternized
vinylpyrrolidone/dialkylaminoalkyl methacrylate copolymers, such as the
products sold under the name "GAFQUAT" by the company ISP, such as, for
example, "GAFQUAT 734" or "GAFQUAT 755" and the products known as
"COPOLYMER 845, 958 and 937". These polymers are described in detail in
French patents 2 077 143 and 2 393 573, the disclosures of which are
incorporated herein by reference;
[0182] dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone
terpolymers, such as the product sold under the name GAFFIX VC 713 by the
company ISP;
[0183] vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such
as the product sold under the name STYLEZE CC 10 by ISP; and
[0184] quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide
copolymers, such as the product sold under the name "GAFQUAT HS 100" by
the company ISP;
[0185] (2) cellulose ether derivatives comprising quaternary ammonium
groups, such as those described in French patent 1,492,597, the
disclosure of which is incorporated herein by reference, and polymers
sold under the names "JR" (JR 400, JR 125 and JR 30M) and "LR" (LR 400,
or LR 30M) by the company Union Carbide Corporation. These polymers are
also defined in the CTFA dictionary as quaternary ammoniums of
hydroxyethylcellulose which have reacted with an epoxide substituted with
a trimethylammonium group;
[0186] (3) cationic cellulose derivatives such as cellulose copolymers and
cellulose derivatives grafted with at least one water-soluble monomer of
quaternary ammonium, such as those described in U.S. Pat. No. 4,131,576,
the disclosure of which is incorporated herein by reference, such as
hydroxyalkylcelluloses (such as, for example, hydroxymethylcelluloses,
hydroxyethylcelluloses and hydroxypropylcelluloses, wherein said
hydroxyalkylcelluloses are grafted with at least one salt chosen from,
for example, methacryloylethyltrimethylammonium salts,
methacrylamidopropyltrimethylammonium salts and dimethyldiallylammonium
salts). For example, commercial products corresponding to the
aforementioned cationic cellulose derivatives include the products sold
under the names "CELQUAT L 200" and "CELQUAT H 100" by the company
National Starch;
[0187] (4) cationic polysaccharides, such as those described in U.S. Pat.
Nos. 3,589,578 and 4,031,307, the disclosures of which are incorporated
herein by reference, such as guar gums comprising at least one cationic
trialkylammonium group. For example, guar gums modified with at least one
salt, such as a chloride salt, of 2,3-epoxypropyltrimethylammonium may be
used in the present invention. Such products are sold in particular under
the trade names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 and JAGUAR C162 by
the company Meyhall;
[0188] (5) polymers comprising (i) at least one piperazinyl unit and (ii)
at least one group chosen from divalent alkylene groups and divalent
hydroxyalkylene groups, wherein said at least one group optionally
comprises at least one chain chosen from straight chains and branched
chains, wherein said at least one chain is optionally interrupted by at
least one entity chosen from oxygen atoms, sulfur atoms, nitrogen atoms,
aromatic rings and heterocyclic rings, the oxidation products of said
polymers and the quaternization products of said polymers. For example,
such polymers are described in French patents 2,162,025 and 2,280,361,
the disclosures of which are incorporated herein by reference;
[0189] (6) water-soluble polyamino amides which may be prepared by at
least one polycondensation reaction of at least one acidic compound and
at least one polyamine compound, wherein said polyamino amides may be
crosslinked with at least one crosslinking agent chosen from
epihalohydrins, diepoxides, dianhydrides, unsaturated dianhydrides,
bis-unsaturated derivatives, bis-halohydrins, bis-azetidiniums,
bis-haloacyldiamines, bis-alkyl halides and oligomers derived from
reaction of at least one difunctional compound with at least one compound
chosen from bis-halohydrins, bis-azetidiniums, bis-haloacyldiamines,
bis-alkyl halides, epihalohydrins, diepoxides and bis-unsaturated
derivatives, wherein said crosslinking agent may be used in a proportion
generally ranging from 0.025 mol to 0.35 mol per amine group of said
polyamino amide, wherein said polyamino amides may optionally be
alkylated, and wherein if said polyamino amides comprise at least one
tertiary amine group, said polyamino amides may optionally be
quaternized. For example, such polymers are described in French patents
2,252,840 and 2,368,508, the disclosures of which are incorporated herein
by reference;
[0190] (7) polyamino amide derivatives derived from condensation of at
least one polyalkylene polyamine with at least one polycarboxylic acid,
followed by alkylation with at least one bifunctional agent. Non-limiting
examples of such polyamino amide derivatives include adipic
acid/dialkylaminohydroxyalkyldialkylenetriamine polymers wherein the
alkyl group comprises from 1 to 4 carbon atoms, such as methyl groups,
ethyl groups and propyl groups. For example, such polymers are described
in French patent 1,583,363, the disclosure of which is incorporated
herein by reference.
[0191] Other non-limiting examples of such derivatives include the adipic
acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under
the name "CARTARETINE F, F4 or F8" by the company Sandoz.
[0192] (8) polymers derived from the reaction of (i) at least one
polyalkylene polyamine comprising two primary amine groups and at least
one secondary amine group with (ii) at least one dicarboxylic acid chosen
from diglycolic acid and saturated aliphatic dicarboxylic acids
comprising from 3 to 8 carbon atoms. According to the present invention,
the molar ratio of the at least one polyalkylene polyamine to the at
least one dicarboxylic acid generally ranges from 0.8:1 to 1.4:1. The
polyamino amide resulting from the above reaction may be reacted with
epichlorohydrin in a molar ratio of epichlorohydrin to the at least one
secondary amine group of the polyamino amide generally ranging from 0.5:1
to 1.8:1. For example, such polymers are described in U.S. Pat. Nos.
3,227,615 and 2,961,347, the disclosures of which are incorporated herein
by reference.
[0193] Polymers of this type are sold in particular under the name
"HERCOSETT 57" by the company Hercules Inc. and under the name "PD 170"
or "DELSETTE 101" by the company Hercules in the case of adipic
acid/epoxypropyl/diethylenetriamine copolymers.
[0194] (9) cyclopolymers of alkyldiallylamine and cyclopolymers of
dialkyldiallylammonium, such as homopolymers and copolymers comprising,
as a constituent of the chain, at least one unit chosen from units of
formulae (VI) and (VI'): 7
[0195] wherein:
[0196] k and t, which may be identical or different, are each chosen from
0 and 1, with the proviso that the sum of k+t is equal to 1;
[0197] R.sub.12, which may be identical or different, are each chosen from
hydrogen atoms and methyl groups;
[0198] R.sub.10 and R.sub.11, which may be identical or different, are
each chosen from alkyl groups comprising from 1 to 22 carbon atoms, such
as from 1 to 4 carbon atoms, hydroxyalkyl groups, such as hydroxy alkyl
groups wherein the alkyl radical comprises from 1 to 5 carbon atoms, and
C.sub.1-C.sub.4 amidoalkyl groups;
[0199] R.sub.10 and R.sub.11, together with the nitrogen atom to which
they are commonly bonded, may additionally form at least one heterocyclic
group, such as piperidyl groups and morpholinyl groups;
[0200] Y.sup.- is an anion, such as bromide, chloride, acetate, borate,
citrate, tartrate, bisulfate, bisulfite, sulfate and phosphate. For
example, such polymers are described in French patent 2,080,759 and in
its Certificate of Addition 2,190,406, the disclosures of which are
incorporated herein by reference.
[0201] Non-limiting examples of the polymers defined above include the
dimethyldiallylammonium chloride homopolymer sold under the name "MERQUAT
100" by the company Calgon (and its homologues of low weight-average
molecular mass) and copolymers of diallyldimethylammonium chloride and of
acrylamide, sold under the name "MERQUAT 550".
[0202] (10) quaternary diammonium polymers comprising repeating units of
formula (VII): 8
[0203] wherein:
[0204] R.sub.13, R.sub.14, R.sub.15 and R.sub.16, which may be identical
or different, are each chosen from aliphatic groups comprising from 1 to
20 carbon atoms, alicyclic groups comprising from 2 to 20 carbon atoms,
arylaliphatic groups comprising from 5 to 20 carbon atoms, and lower
hydroxyalkyl groups; and
[0205] additionally at least two of said R.sub.13, R.sub.14, R.sub.15 and
R.sub.16, together with the nitrogen atoms to which they are attached,
may form at least one heterocycle optionally comprising an additional
heteroatom other than nitrogen; and
[0206] additionally, R.sub.13, R.sub.14, R.sub.15 and R.sub.16, which may
be identical or different, may each be chosen from linear and branched
C.sub.1-C.sub.6 alkyl groups substituted with at least one group chosen
from nitrile groups, ester groups, acyl groups, amide groups and groups
chosen from groups of formulae --CO--O--R.sub.17--D and
--CO--NH--R.sub.17--D wherein R.sub.17 is chosen from alkylene groups and
D is chosen from quaternary ammonium groups;
[0207] A.sub.1 and B.sub.1, which may be identical or different, are each
chosen from polymethylene groups comprising from 2 to 20 carbon atoms,
chosen from linear and branched, saturated and unsaturated polymethylene
groups wherein said polymethylene groups may optionally comprise,
optionally linked to and optionally intercalated in the main chain, at
least one entity chosen from aromatic rings, oxygen atoms, sulfur atoms,
sulfoxide groups, sulfone groups, disulfide groups, amino groups,
alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido
groups, amide groups and ester groups; and
[0208] X.sup.- is an anion chosen from anions derived from inorganic acids
and anions derived from organic acids; and
[0209] A.sub.1, R.sub.13 and R.sub.15 may optionally form, together with
the nitrogen atoms to which they are attached, at least one piperazine
ring;
[0210] with the proviso that if A.sub.1 is chosen from linear and
branched, saturated and unsaturated alkylene groups and linear and
branched, saturated and unsaturated hydroxyalkylene groups, B.sub.1 may
also be chosen from groups of formula:
--(CH.sub.2).sub.n--CO--D--OC--(CH.sub.2).sub.n--
[0211] wherein:
[0212] n is a number such that the overall quaternary diammonium polymer
has a number-average molecular mass generally ranging for example from
1000 to 100,000;
[0213] D is chosen from:
[0214] a) glycol residues of formula: --O--Z--O--, wherein Z is chosen
from linear and branched hydrocarbon groups and groups chosen from groups
of formulae:
--(CH.sub.2--CH.sub.2--O).sub.x--CH.sub.2--CH.sub.2--;
and
--[CH.sub.2--CH(CH.sub.3)--O].sub.y--CH.sub.2--CH(CH.sub.3)--
[0215] wherein x and y, which may be identical or different, are each
chosen from integers ranging from 1 to 4 (in which case x and y represent
a defined and unique degree of polymerization) and any number ranging
from 1 to 4 (in which case x and y represent an average degree of
polymerization);
[0216] b) bis-secondary diamine residues such as piperazine derivatives;
[0217] c) bis-primary diamine residues chosen from residues of formula:
--NH--Y--NH--, wherein Y is chosen from linear and branched hydrocarbon
groups and residues of formula --CH.sub.2--CH.sub.2--S--S--CH.sub.2--CH.s-
ub.2--; and
[0218] d) ureylene groups of formula: --NH--CO--NH--.
[0219] In one embodiment, X.sup.- is an anion chosen from chloride ions
and bromide ions. According to the present invention, the quarternary
diammonium polymers have a number-average molecular mass generally
ranging from 1000 to 100,000.
[0220] For example, polymers of this type are described in French Patent
Nos. 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and U.S.
Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462,
2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904,
4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020, the
disclosures of which are incorporated herein by reference.
[0221] Further, according to the present invention, polymers comprising
repeating units of formula (a) may be used: 9
[0222] wherein:
[0223] R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which may be identical or
different, are each chosen from alkyl groups comprising from 1 to 4
carbon atoms and hydroxyalkyl groups comprising from 1 to 4 carbon atoms;
[0224] n and p, which may be identical or different, are each chosen from
integers ranging from 2 to 20; and
[0225] X.sup.- is an anion chosen from anions derived from inorganic acids
and anions derived from organic acids.
[0226] (11) polyquaternary ammonium polymers comprising repeating units of
formula (VIII): 10
[0227] wherein:
[0228] p is an integer ranging from 1 to 6,
[0229] D is chosen from direct bonds and --(CH.sub.2).sub.r--CO-- groups,
wherein r is a number equal to 4 or 7, and
[0230] X.sup.- is an anion chosen from anions derived from inorganic acids
and anions derived from organic acids.
[0231] For example, such compounds are described in patent application
EP-A-122,324, the disclosure of which is incorporated by reference
herein, and may be prepared according to the procedures described in the
U.S. Pat. Nos. 4,157,388, 4,390,689, 4,702,906, and 4,719,282, the
disclosures of which are incorporated by reference herein.
[0232] Among these, there may be mentioned for example the products
"Mirapol A 15", "Mirapol AD1", "Mirapol AZ1" and Mirapol 175" sold by the
company Miranol.
[0233] (12) quaternary polymers of vinylpyrrolidone and quaternary
polymers of vinylimidazole, such as, for example, the products sold under
the names LUVIQUAT FC 905, FC 550 and FC 370 by the company BASF.
[0234] (13) polyamines, such as POLYQUART H sold by Henkel under the
reference name "POLYETHYLENE GLYCOL (15) TALLOW POLYAMINE" in the CTFA
dictionary.
[0235] (14) crosslinked (meth)acryloyloxy(C.sub.1-C.sub.4)alkyltri(C.sub.1-
-C.sub.4)alkylammonium salt polymers, such as the polymers derived from
homopolymerization of dimethylaminoethyl methacrylate quaternized with
methyl chloride and polymers derived from copolymerization, for example,
of acrylamide with dimethylaminoethyl methacrylate quaternized with a
methyl halide (such as methyl chloride), wherein the homo- or
copolymerization is followed by crosslinking with at least one compound
comprising olefinic unsaturation, such as methylenebisacrylamide. For
example, a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium
chloride copolymer (20/80 by weight) in the form of a dispersion
comprising about 50% by weight of said copolymer in mineral oil may be
used. This dispersion is sold under the name "SALCARE SC 92" by the
company Allied Colloids. Further, a crosslinked methacryloyloxyethyltrime-
thylammonium chloride homopolymer comprising about 50% by weight of the
homopolymer in mineral oil or in a liquid ester may be used. These
dispersions are sold under the names "SALCARE SC 95" and "SALCARE SC 96"
by the company Allied Colloids.
[0236] Other cationic polymers which may be used as the at least one
cationic polymer according to the present invention are
polyalkyleneimines (such as polyethyleneimines), polymers comprising at
least one vinylpyridine unit, polymers comprising at least one
vinylpyridinium unit, condensates of polyamines, condensates of
epichlorohydrin, quaternary polyureylenes and chitin derivatives.
[0237] Other embodiments of the invention use cationic polymers chosen
from the polymers of (1), (9), (10), (11) and (14). Specifically,
polymers of formulae (W) and (U) can be used: 11
[0238] such as those of which the molecular weight, determined by gel
chromatography, ranges from 9500 to 9900; 12
[0239] and in particular those of which the molecular weight, determined
by gel chromatography, is approximately 1200.
[0240] Generally, the cationic polymers are present in an amount ranging
for example from 0.01% to 10% by weight, such as from 0.05% to 5% by
weight and further such as from 0.1% to 3% by weight, relative to the
total weight of the final composition.
[0241] Amphoteric polymers
[0242] The amphoteric polymers which can be used in the present invention
can be chosen from polymers comprising K and M units distributed
statistically in the polymer chain, wherein:
[0243] K is a unit derived from a monomer comprising at least one basic
nitrogen atom and M is a unit derived from an acid monomer comprising at
least one group chosen from carboxylic groups and sulfonic groups; or
alternatively
[0244] K and M, which are identical or different, are each groups chosen
from groups derived from zwitterionic monomers of carboxybetaines and
groups derived from zwitterionic monomers of sulfobetaines; or
alternatively
[0245] K and M, which are identical or different, are each chosen from
polymers comprising cationic polymer chains comprising at least one amine
group chosen from primary, secondary, tertiary and quaternary amine
groups, wherein at least one of the amine groups is substituted with a
group chosen from carboxylic groups and sulphonic groups linked via a
hydrocarbon radical; or alternatively
[0246] K and M form part of a chain of a polymer with an
.alpha.,.beta.-dicarboxylic ethylene unit wherein one of the carboxylic
groups has been caused to react with a polyamine comprising at least one
amine group chosen from primary amine groups and secondary amine groups.
[0247] Representative of the film forming amphoteric polymers defined
above that can be used include the following polymers:
[0248] (1) The polymers resulting from the copolymerization of a monomer
derived from a vinyl compound substituted with a carboxylic group such as
acrylic acid, methacrylic acid, maleic acid, and .alpha.-chloroacrylic
acid, and of a basic monomer derived from a substituted vinyl compound
comprising at least one basic atom such as dialkylaminoalkyl methacrylate
and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Such
compounds are described in U.S. Pat. No. 3,836,537, the disclosure of
which is incorporated by reference herein. Copolymer of the sodium
acrylate/acrylamidopropyl-trimethylammonium chloride sold under the name
of "POLYQUART KE 3033" by the company HENKEL can also be cited.
[0249] The vinyl compound can also be a salt of dialkyldiallylammonium
such as diethyldiallylammonium chloride. The copolymers of acrylic acid
and the latter monomer are proposed under the name "MERQUAT 280",
"MERQUAT 295" and "MERQUAT PLUS 3330" by the company CALGON.
[0250] (2) The polymers comprising units derived from:
[0251] a) at least one monomer chosen from acrylamides substituted on the
nitrogen by an alkyl radical and methacrylamides substituted on the
nitrogen by an alkyl radical,
[0252] b) at least one acidic comonomer comprising at least one reactive
carboxylic group, and
[0253] c) at least one basic comonomer such as comonomers chosen from
esters of acrylic acid and esters of methacrylic acid, said esters being
substituted with at least one amine chosen from primary, secondary,
tertiary and quaternary amines, and the product of quaternization of
dimethylaminoethyl methacrylate with a sulfate chosen from dimethyl
sulfate and diethyl sulfate.
[0254] Some embodiments according to the invention utilize N-substituted
acrylamides and methacrylamides comprising (C.sub.2-C.sub.12)alkyl
groups, such as N-ethylacrylamide, N-tert-butylacrylamide,
N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, and
N-dodecylacrylamide, as well as the corresponding methacrylamides.
[0255] The acidic comonomers can be chosen, for example, from acrylic,
methacrylic, crotonic, itaconic, maleic and fumaric acids as well as the
(C.sub.1-C.sub.4)alkyl monoesters of entities chosen from maleic
anhydride, fumaric anhydride, maleic acid, and fumaric acid.
[0256] The basic comonomers can be chosen, for example, from methacrylates
of aminoethyl, butylaminoethyl, N,N'-dimethylaminoethyl, and
N-tert-butylaminoethyl.
[0257] Additionally, the copolymers having the CTFA name (4.sup.th
edition, 1991) Octylacrylamide/acrylates/butylaminoethylmethacrylate
copolymer such as the products sold under the name AMPHOMER and LOVOCRYL
47 by the company NATIONAL STARCH can also be used.
[0258] (3) The partially and completely alkylated and crosslinked
polyaminoamides derived from polyaminoamides of formula:
CO--R.sub.27--CO--Z (VIII)
[0259] wherein:
[0260] R.sub.27 is a divalent group chosen from groups derived from
saturated dicarboxylic acids, groups derived from dicarboxylic aromatic
acids, groups derived from mono- and dicarbocylic aliphatic acids
comprising at least one ethylenic double bond, groups derived from an
ester of (C.sub.1-C.sub.6)alkanols of said acids, and groups derived from
the addition of any one of said aforementioned acids with an amine chosen
from bis-primary and bis-secondary amines, and
[0261] Z is a divalent group derived from polyalkylene-polyamines chosen
from bis-primary, mono- and bis-secondary polyalkylene-polyamines, for
example, Z represents:
[0262] a) in an amount ranging from 60 mol % to 100 mol %, the group 13
[0263] wherein x=2 and p=2 or 3, or alternatively x=3 and p=2,
[0264] it being understood that group Z of formula a) is derived from a
compound chosen from diethylenetriamine, triethylenetetraamine and
dipropylenetriamine;
[0265] b) in an amount ranging from 0 mol % to 40 mol %, (1) said groups
(IX) above in which x=2 and p=1 and which said group is derived from a
compound chosen from ethylenediamine, and (2) groups derived from
piperazine: 14
[0266] c) in an amount ranging from 0 mol % to 20 mol %,the
polyalkylene-polyamine group --NH--(CH.sub.2).sub.6--NH--, which is
derived from hexamethylenediamine, wherein said polyalkylene-polyamine
group is crosslinked by adding a bifunctional crosslinking agent (chosen
from the epihalohydrins, diepoxides, dianhydrides, and bis-unsaturated
derivatives) present in an amount ranging from 0.025 mol to 0.35 mol of
crosslinking agent per amine group of the polyamino amide and alkylated
by the action of at least one compound chosen from acrylic acid,
chloroacetic acid, alkanesultones, and salts thereof.
[0267] The saturated dicarboxylic acids are for example chosen from
saturated (C.sub.6-C.sub.10) dicarboxylic acids such as adipic,
2,2,4-trimethyladipic and 2,4,4-trimethyladipic acid.
[0268] Representative dicarboxylic aromatic acids include for example
(C.sub.6-C.sub.10) dicarboxylic aromatic acids, such as terephthalic
acid. And representative mono- and dicarboxylic aliphatic acids
comprising at least one ethylenic double bond include for example
acrylic, methacrylic and itaconic acids.
[0269] The alkanesultones used in the alkylation can, for example, be
chosen from propanesultone and butanesultone, and the salts of the
alkylating agents can be chosen from sodium and potassium salts of said
alkylating agents.
[0270] (4) The polymers comprising zwitterionic units of formula: 15
[0271] wherein:
[0272] R.sub.28 is chosen from polymerizable unsaturated groups such as
acrylate, methacrylate, acrylamide and methacrylamide groups,
[0273] y and z, which can be identical or different, are each chosen from
integers ranging from 1 to 3,
[0274] R.sub.29 and R.sub.30, which may be identical or different, are
each chosen from hydrogen, and methyl, ethyl and propyl groups,
[0275] R.sub.31 and R.sub.32, which may be identical or different, are
each chosen from hydrogen and alkyl groups, provided that the sum of the
carbon atoms in R.sub.31, and R.sub.32 does not exceed 10.
[0276] The polymers comprising such units may also comprise units derived
from nonzwitterionic monomers such as dimethylaminoethyl acrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl acrylate,
diethylaminoethyl methacrylate, alkyl acrylates, alkyl methacrylates,
alkyl acrylamides, alkyl methacrylamides, and vinyl acetate. By way of
example, there may be mentioned the copolymer of methyl
methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate such
as the product sold under the name DIAFORMER Z301 by the company SANDOZ.
[0277] (5) The polymers derived from chitosan comprising at least one
monomeric unit chosen from formulae (D), (E) and (F), which are described
for example in U.S. Pat. No. 4,996,059, the disclosure of which is herein
incorporated by reference: 16
[0278] wherein said unit (D) is present in an amount ranging for example
from 0% to 30%, by weight relative to the total weight of said polymer,
said unit (E) is present in an amount ranging for example from 5% to 50%
by weight relative to the total weight of said polymer, and said unit (F)
is present in an amount ranging for example from 30% to 90% by weight
relative to the total weight of said polymer,
[0279] and wherein in said unit (F), R.sub.33 is chosen from groups of
formula: 17
[0280] wherein:
[0281] q is equal to 0 or 1, and (i) when q is equal to 0, R.sub.34,
R.sub.35, and R.sub.36, which may be identical or different, are each
chosen from:
[0282] hydrogen,
[0283] methyl, hydroxyl, acetoxy, and amino groups,
[0284] monoalkylamine and dialkylamine groups optionally interrupted by at
least one nitrogen atom and/or optionally substituted with at least one
group chosen from amine, hydroxyl, carboxyl, alkylthio and sulfonic
groups, and
[0285] alkylthio groups wherein said alkyl portion of said alkylthio group
carries an amino group,
[0286] provided that at least one of said R.sub.34, R.sub.35 and R.sub.36
groups is chosen from hydrogen; and
[0287] (ii) when q is equal to 1, R.sub.34, R.sub.35 and R.sub.36, which
may be identical or different, are each chosen from hydrogen,
[0288] and the salts formed by these polymers (5) with bases, and the
salts formed by these polymers (5) with acids.
[0289] (6) The polymers derived from the N-carboxyalkylation of chitosan
such as N-carboxymethyl chitosan and N-carboxybutyl chitosan sold under
the name "EVALSAN" by the company JAN DEKKER.
[0290] (7) The polymers of formula (XI), which are described for example
in French Patent 1 400366, the disclosure of which is incorporated by
reference herein: 18
[0291] wherein:
[0292] r is chosen such that the number-average molecular weight of said
polymer ranges from 500 to 6,000,000, such as from 1000 to 1,000,000.
[0293] R.sub.37 is chosen from hydrogen and CH.sub.3O, CH.sub.3CH.sub.2O,
and phenyl groups,
[0294] R.sub.38 and R.sub.39, which are identical or different, are each
chosen from hydrogen and lower alkyl groups such as methyl and ethyl,
[0295] R.sub.40 is chosen from lower alkyl groups such as methyl and ethyl
and groups of formula: --R.sub.41--N(R.sub.39).sub.2, comprising up to 6
carbon atoms, wherein R.sub.39 is as defined above and R.sub.41 is
defined below,
[0296] R.sub.41 is chosen from --CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--CH.sub.2--, and --CH.sub.2--CH(CH.sub.3)--.
[0297] (8) Amphoteric polymers of the --D--X--D--X-- type, which are
described for example in U.S. Pat. No. 4,996,059, the disclosure of which
is herein incorporated by reference, chosen from:
[0298] a) polymers derived from reaction of chloroacetic acid or sodium
chloroacetate with at least one compound comprising at least one unit of
formula (XII):
--D--X--D--X--D-- (XI)
[0299] wherein D is a group: 19
[0300] and X is chosen from the symbols E and E', wherein E and E', which
are identical or different, are each chosen from bivalent groups chosen
from alkylene groups comprising at least one chain chosen from linear and
branched chains comprising up to 7 carbon atoms in the principal chain,
wherein said principal chain is optionally substituted with at least one
hydroxyl group, and wherein said alkylene groups optionally comprise at
least one atom chosen from oxygen atoms, nitrogen atoms and sulfur atoms,
wherein said at least one optional atom is present in the form of at
least one group chosen from ether, thioether, sulfoxide, sulfone,
sulfonium, alkylamine and alkenylamine groups, and hydroxyl, benzylamine,
amine oxide, quaternary ammonium, amide, imide, alcohol, ester and
urethane groups, and wherein said alkylene groups optionally comprise 1
to 3 rings chosen from aromatic rings and heterocyclic rings,
[0301] b) polymers of formula:
--D--X--D--X-- (XIII)
[0302] wherein:
[0303] D is a group: 20
[0304] X is chosen from the symbols E and E' and wherein at least one X
is chosen from E',
[0305] E is chosen from bivalent groups chosen from alkylene groups
comprising at least one chain chosen from linear and branched chains
comprising up to 7 carbon atoms in the principal chain, wherein said
principal chain is optionally substituted with at least one hydroxyl
group, and wherein said alkylene groups optionally comprise at least one
atom chosen from oxygen atoms, nitrogen atoms, and sulfur atoms, wherein
said at least one optional atom is present in the form of at least one
group chosen from ether, thioether, sulfoxide, sulfone, sulfonium,
alkylamine and alkenylamine groups, and hydroxyl, benzylamine, amine
oxide, quaternary ammonium, amide, imide, alcohol, ester and urethane
groups, and wherein said alkylene groups optionally comprise 1 to 3 rings
chosen from aromatic rings and heterocyclic rings, and
[0306] E' is a bivalent group chosen from alkylene groups comprising at
least one chain chosen from linear and branched chains comprising up to 7
carbon atoms in the principal chain, wherein said principal chain is
optionally substituted with at least one hydroxyl group, and wherein said
alkylene groups comprise at least one nitrogen atom substituted with an
alkyl chain, wherein said alkyl chain is optionally interrupted by an
oxygen atom and, wherein said alkyl chain comprises at least one
functional group chosen from carboxyl and hydroxyl functional groups, and
wherein said at least one alkyl chain is betainized by reaction with a
reactant chosen from chloroacetic acid and sodium chloroacetate.
[0307] (9) The copolymers (C.sub.1-C.sub.5)alkyl vinyl ether/maleic
anhydride partially modified by semiamidation with an
N,N-dialkylaminoalkylamine such as N,N-dimethylaminopropylamine or by
semiesterification with an N,N-dialkanolamine. These copolymers may also
comprise other vinyl comonomers such as vinylcaprolactam.
[0308] The amphoteric polymers of family (1) are utilized in certain
embodiments of the invention.
[0309] According to the invention, the at least one polymer chosen from
cationic and amphoteric polymers may be present in an amount ranging for
example from 0.01% to 10% by weight relative to the total weight of the
composition, such as from 0.05% to 5% by weight relative to the total
weight of the composition, and further such as from 0.1% to 3% by weight
relative to the total weight of the composition.
[0310] Surfactants
[0311] The ready-to-use composition according to the invention can
comprise at least one surfactant, which is present in at least one of
said at least one dyeing composition (A), said at least one oxidizing
composition (B), and said at least one dyeing composition (A) and said at
least one oxidizing composition (B).
[0312] The at least one surfactant may be chosen from anionic, amphoteric,
nonionic, zwitterionic and cationic surfactants.
[0313] Representative choices for the at least one surfactant include the
following:
[0314] (i) Anionic surfactant(s):
[0315] Representative anionic surfactants include salts (for example
alkaline salts, such as sodium salts, ammonium salts, amine salts, amino
alcohol salts and magnesium salts) of the following compounds: alkyl
sulfates, alkyl ether sulfates, alkylamidoether sulfates,
alkylarylpolyether sulfates, monoglyceride sulfates; alkyl sulfonates,
alkyl phosphates, alkylamide sulfonates, alkylaryl sulfonates,
.alpha.-olefin sulfonates, paraffin sulfonates; alkyl(C.sub.6-C.sub.24)
sulfosuccinates, alkyl(C.sub.6-C.sub.24) ether sulfosuccinates,
alkyl(C.sub.6-C.sub.24)amide sulfosuccinates, alkylsulfosuccinamates
alkyl(C.sub.6-C.sub.24) sulfoacetates, acyl(C.sub.6-C.sub.24)
sarcosinates, acyl(C.sub.6-C.sub.24) glutamates, acyl isethionates,
N-acyltaurates, and alkyl(C.sub.6-C.sub.24)polyglycoside carboxylic
esters such as alkylglucoside citrates, alkylpolyglycoside tartrate,
alkylpolyglycoside sulfosuccinates, and alkyl sulfosuccinamates. The
alkyl and acyl radicals of all of these various compounds can for example
comprise from 12 to 20 carbon atoms, and the aryl radicals can for
example be chosen from phenyl and benzyl groups.
[0316] For example, anionic surfactants can be chosen from fatty acid
salts such as the salts of oleic acid, ricinoleic acid, palmitic acid,
stearic acid, the acids of copra oil and the acids of hydrogenated copra
oil, and acyl lactylates in which the acyl radical comprises from 8 to 20
carbon atoms. At least one weakly anionic surfactant can also be used,
such as alkyl-D-galactosideuronic acids and their salts, as well as
polyoxyalkylenated carboxylic (C.sub.6-C.sub.24)alkyl ether acids,
polyoxyalkylenated carboxylic (C.sub.6-C.sub.24)alkylaryl ether acids,
polyoxyalkylenated carboxylic (C.sub.6-C.sub.24)alkyl amidoether acids
and their salts, for example, those comprising from 2 to 50 ethylene
oxide groups.
[0317] (ii) Nonionic surfactant(s):
[0318] Useful nonionic surfactants include compounds that are well known
per se (see for example in this respect "Handbook of Surfactants" by M.
R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp.
116-178), the disclosure of which is incorporated by reference herein.
Thus, nonionic surfactants can include alcohols, .alpha.-diols, and
polyethoxylated alkylphenols and polypropoxylated alkylphenols comprising
at least one fatty chain comprising for example from 8 to 18 carbon
atoms, wherein the number of ethylene oxide and propylene oxide groups
can range for example from 2 to 50. Additionally, copolymers of ethylene
oxide, copolymers of propylene oxide, condensates of ethylene oxide with
fatty alcohols, condensates of propylene oxide with fatty alcohols,
polyethoxylated fatty amides, such as those comprising from 2 to 30 mol
of ethylene oxide, polyglycerolated fatty amides on average comprising 1
to 5 glycerol groups, such as from 1.5 to 4, polyethoxylated fatty amines
comprising for example from 2 to 30 mol of ethylene oxide, oxyethylenated
fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene
oxide, fatty acid esters of sucrose, fatty acid esters of polyethylene
glycol, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides,
such as the oxides of (C.sub.10-C.sub.14) alkylamines, and
N-acylaminopropylmorpholine oxides can also be used. It will be noted
that the alkylpolyglycosides are nonionic surfactants that can be
suitable in the context of the present invention.
[0319] (iii) Amphoteric or zwitterionic surfactant(s):
[0320] Representative amp
hoteric and zwitterionic surfactants can be
chosen from aliphatic secondary and tertiary amine derivatives in which
the aliphatic radical is chosen from linear and branched chain radicals
comprising 8 to 18 carbon atoms and comprising at least one water-soluble
anionic group (chosen for example from carboxylate, sulfonate, sulfate,
phosphate and phosphonate); mention may also be made of
(C.sub.8-C.sub.20)alkylbetaines, sulfobetaines, (C.sub.8-C.sub.20)alkylam-
ido(C.sub.1-C.sub.6)alkylbetaines and (C.sub.8-C.sub.20)alkylamido(C.sub.1-
-C.sub.6)alkylsulfobetaines. Representative amine derivatives include the
products sold under the name MIRANOL, as described in U.S. Pat. Nos.
2,528,378 and 2,781,354, the disclosures of which are incorporated by
reference herein, and classified in the CTFA dictionary, 3.sup.rd
edition, 1982, under the names Amphocarboxyglycinates and
Amphocarboxypropionates, having the respective structures:
R.sub.2--CONHCH.sub.2CH.sub.2--N.sup.+(R.sub.3)(R.sub.4)(CH.sub.2COO--)
(2)
[0321] in which:
[0322] R.sub.2 is chosen from alkyl groups derived from an acid
R.sub.2--COOH present in hydrolysed copra oil, and heptyl, nonyl and
undecyl radicals, --R.sub.3 is a beta-hydroxyethyl group, and --R.sub.4
is a carboxymethyl group; and
R.sub.5--CONHCH.sub.2CH.sub.2--N(B)(C) (3)
[0323] in which:
[0324] (B) is --CH.sub.2CH.sub.2OX', wherein X' is an entity chosen from a
--CH.sub.2CH.sub.2--COOH group and a hydrogen atom,
[0325] (C) is --(CH.sub.2).sub.z--Y', wherein z=1 or 2, and wherein Y' is
an entity chosen from --COOH and --CH.sub.2--CHOH--SO.sub.3H groups,
[0326] R.sub.5 is chosen from alkyl groups, such as (a) alkyl groups of an
acid R.sub.5--COOH present in oils chosen from copra oil and hydrolysed
linseed oil, (b) alkyl groups, such as C.sub.7, C.sub.9, C.sub.11 and
C.sub.13 alkyl groups, and (c) C.sub.17 alkyl groups and the iso forms,
and unsaturated C.sub.17 groups.
[0327] Such representative compounds are classified in the CTFA
dictionary, 5th edition, 1993, under the names disodium
cocoamphodiacetate, disodium lauroamphodiacetate, disodium
caprylamphodiacetate, disodium capryloamphodiacetate, disodium
cocoamphodipropionate, disodium lauroamphodipropionate, disodium
caprylamphodipropionate, disodium capryloamphodipropionate,
lauroamphodipropionic acid, and cocoamphodipropionic acid. By way of
example, mention may be made of the cocoamphodiacetate sold under the
trade name MIRANOL C2M Concentrate by the company RHODIA CHIMIE.
[0328] (iv) Cationic surfactants:
[0329] Representative cationic surfactants include salts of optionally
polyoxyalkylenated primary, secondary and tertiary fatty amines;
quaternary ammonium salts such as tetraalkylammonium,
alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, and
trialkylhydroxyalkylammonium, alkylpyridinium chlorides, alkylpyridinium
bromides, imidazoline derivatives; and amine oxides of cationic nature.
[0330] In one embodiment, in the ready-to-use composition according to the
invention, the dyeing composition (A) comprises at least one nonionic
surfactant.
[0331] The at least one surfactant may be present in the composition
according to the invention generally in an amount ranging for example
from 0.01% to 40% by weight relative to the total weight of the
composition, such as from 0.1% to 30% by weight relative to the total
weight of the composition.
[0332] The ready-to-use composition according to the present invention may
eventually comprise, in composition (A), composition (B), or both
compositions (A) and (B), at least one other agent for adjustment of
rheology, such as agents chosen from cellulose thickeners (for example,
hydroxyethylcellulose, hydroxypropylcellulose, and
carboxymethylcellulose), guar gum and its derivatives (for example,
hydroxypropylguar), gums of microbial origin (for example, xanthan gum
and scleroglucan gum), and synthetic thickeners (for example, crosslinked
homopolymers of acrylic acid and crosslinked homopolymers of
acrylamidopropanesulfonic acid.
[0333] Generally, these thickeners may be present in an amount ranging for
example from 0.01% to 10% by weight relative to the total weight of the
composition.
[0334] The medium of the composition appropriate for dyeing can be an
aqueous medium, optionally comprising at least one cosmetically
acceptable organic solvent.
[0335] Representative organic solvents may be chosen from alcohols, such
as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl
alcohol. The organic solvents may also be chosen from glycols (for
example, ethyleneglycol, propyleneglycol, butyleneglycol,
dipropyleneglycol, and diethyleneglycol) and ethers of glycols (for
example, monomethyl, monoethyl and monobutyl ethers of ethyleneglycol and
for example monomethyl ether of propyleneglycol and alkyl ethers of
diethyleneglycol glycol, such as, for example, monoethylether and
monobutylether of diethyleneglycol).
[0336] The organic solvents are generally present in an amount ranging for
example from 0.5% to 20% by weight relative to the total weight of the
composition, such as from 2% to 10% by weight relative to the total
weight of the composition.
[0337] The composition according to the invention may further comprise an
effective quantity of other agents. For example, agents that are already
known for oxidation coloration, such as various ordinary adjuvants
including sequesterizers such as EDTA and etidronic acid, UV-screening
agents, waxes, volatile and nonvolatile, cyclic and non-cyclic, linear
and branched, organomodified (such as by amine groups) silicones,
preservatives, ceramides, pseudoceramides, vegetable, mineral and
synthetic oils, vitamins and provitamins such as panthenol, and
opacifiers, may be included.
[0338] The composition can also comprise at least one agent chosen from
reducing agents and antioxidants. Representative additional agents may
include sodium sulfite, thioglycolic acid, thiolactic acid, sodium
bisulfite, dehydroascorbic acid, hydroquinone, 2-methylhydroquinone,
tert-butylhydroquinone and homogentisic acid. Generally, such agents may
be present in the an amount ranging for example from 0.05% to 3.0% by
weight relative to the total weight of the composition, such as from
0.05% to 1.5% by weight relative to the total weight of the composition.
[0339] The composition according to the invention may also comprise at
least one fatty alcohol comprising at most twenty carbon atoms.
Representative fatty alcohols comprising at most twenty carbon atoms that
may be used include lauryl, cetyl, stearyl and oleyl alcohols. These
additional fatty alcohols may be present in an amount ranging for example
from 0.001% to 20% by weight relative to the total weight of the
composition.
[0340] One skilled in the art should take care to select said optionally
complementary compounds, such that the advantageous properties
intrinsically associated with the dye composition according to the
invention are not, or are not substantially, adversely affected by the
additions envisaged.
[0341] In the ready-to-use composition, said at least one composition (B)
may comprise at least one oxidizing agent chosen, for example, from
hydrogen peroxide, urea peroxide, alkali metal bromates and
ferricyanides, and persalts such as perborates and persulfates. More
specifically, hydrogen peroxide may be used. This oxidizing agent is
advantageously constituted by an oxygenated aqueous solution of which the
titre may range from 1 to 40 in volume, such as from 5 to 40.
[0342] As an oxidizing agent, at least one oxidation-reduction enzyme such
as laccases, peroxydases and 2-electron oxydoreductases (such as
uricase), if necessary in the presence of their respective donor or
cofactor, may also be used.
[0343] The pH of the dyeing composition (A) or of the ready-to-use
composition applied to the keratin fibers [composition resulting from
mixing the dye composition (A) and the oxidizing composition (B)],
generally ranges from 4 to 12, such as from 6 to 11, and may be adjusted
to the desired value by means of at least one agent chosen from
acidifying and basifying agents well-known in the art of dyeing keratin
fibers.
[0344] Representative basifying agents include aqueous ammonia, alkali
metal carbonates, alkanolamines such as mono-, di- and triethanolamines
and derivatives thereof, hydroxyalkylamines and oxyethylenated and
oxypropylenated ethylenediamines, sodium and potassium hydroxide and
compounds of formula (XIV): 21
[0345] wherein:
[0346] R is a propylene residue optionally substituted with a group chosen
from hydroxyl and C.sub.1-C.sub.4 alkyl groups;
[0347] R.sub.42, R.sub.43, R.sub.44 and R.sub.45, which may be identical
or different, are each chosen from hydrogen, C.sub.1-C.sub.4 alkyl groups
and C.sub.1-C.sub.4 hydroxyalkyl groups.
[0348] Representative acidifying agents include, classically, by way of
example, organic and inorganic acids such as hydrochloric acid,
orthophosphoric acid, and carboxylic acids such as tartaric acid, citric
acid, lactic acid and sulfonic acids.
[0349] One dyeing method according to the invention comprises applying on
dry or wet keratin fibers, such as human keratin fibers like hair, at
least one ready-to-use cosmetic composition, prepared at the time of use
from at least one dyeing composition (A) and at least one oxidizing
composition (B), leaving said at least one ready-to-use composition on
said keratin fibers for a time ranging from 1 to 60 minutes, such as from
10 to 45 minutes, rinsing said keratin fibers, optionally shampooing said
keratin fibers, rinsing said keratin fibers after said optional
shampooing, and drying said keratin fibers, wherein said at least one
ready-to-use cosmetic composition comprises:
[0350] at least one composition (A) comprising, in a dyeing medium:
[0351] (1) at least one oxidation dye,
[0352] (2) at least one thickening polymer comprising at least one fatty
chain, and
[0353] (3) at least one fatty alcohol comprising more than twenty carbon
atoms, and
[0354] at least one composition (B) comprising at least one oxidizing
agent.
[0355] Another process comprises applying on dry or wet keratin fibers,
such as human keratin fibers like hair, at least one ready-to-use
cosmetic composition, prepared at the time of use from at least one
composition (A'), at least one composition (A"), and at least one
oxidizing composition (B), leaving said at least one ready-to-use
composition on said keratin fibers for a resting time ranging from 1 to
60 minutes, such as from 10 to 45 minutes, rinsing said keratin fibers,
optionally shampooing said keratin fibers, and after said optional
shampooing again rinsing and drying said keratin fibers, wherein said
composition comprises:
[0356] at least one composition (A') comprising at least one oxidation dye
and at least one fatty alcohol comprising more than twenty carbon atoms,
[0357] at least one composition (A") comprising at least one thickening
polymer comprising at least one fatty chain,
[0358] at least one composition (B) comprising at least one oxidizing
agent, and
[0359] wherein said composition comprising said at least one compositions
(A'), (A") and (B) is prepared by mixing said at least one compositions
(A'), (A"), and (B) at the moment of use.
[0360] Unless otherwise indicated, all numbers expressing quantities of
ingredients, properties such as molecular weight, reaction conditions,
and so forth used in the specification and claims are to be understood as
being modified in all instances by the term "about." Accordingly, unless
indicated to the contrary, the numerical parameters set forth in the
following specification and attached claims are approximations that may
vary depending upon the desired properties sought to be obtained by the
present invention. At the very least, and not as an attempt to limit the
application of the doctrine of equivalents to the scope of the claims,
each numerical parameter should at least be construed in light of the
number of reported significant digits and by applying ordinary rounding
techniques. Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations, the
numerical values set forth in the specific examples are reported as
precisely as possible. Any numerical value, however, inherently contain
certain errors necessarily resulting from the standard deviation found in
their respective testing measurements.
[0361] Concrete examples illustrating the invention are indicated below
without however exhibiting a limiting character.
EXAMPLES
[0362] The following compositions were prepared:
1
Oxidizing composition:
Fatty
alcohol 2.3 g
Oxyethylenated fatty alcohol 0.6 g
Fatty
amide 0.9 g
Glycerin 0.5 g
Hydrogen peroxide 7.5 g
Perfume qs
Demineralized water qs 100 g
[0363]
2
Dyeing composition:
(expressed in grams)
Mixture of C.sub.18 to C.sub.24 linear alcohols
[C.sub.18/C.sub.20/C.sub.22/C.sub.24, 7/58/30/6] 3
(NAFOL 20-22)
Mixture of oxyethylenated C.sub.18 to C.sub.24 linear alcohols
[C.sub.18/C.sub.20/C.sub.22/C.sub.24, 1.35
7/58/30/6] 30 EO
(NAFOLOX 20-22 30EO)
Oxyethylenated stearyl alcohol 2 EO 4
Oxyethylenated stearyl alcohol 21 EO 2
Oleic acid 2.6
Glycol distearate 2
Propylene glycol 5
Monoisopropanolamide
of copra acids 2
Aculyn 44 sold by the company ROHM & HAAS 1.4 AS*
Crosslinked polyacrylic acid 0.6
Cationic polymer of
formula (W) 3 AS*
Merquat 100 sold by the company CALGON 0.4 AS*
Reducing agents 0.7
Seqestrants 0.2
1,3-Dihydroxybenzene (resorcinol) 0.6
1,4-Diaminobenzene 0.5
1-Hydroxy-3-aminobenzene 0.1
1-Hydroxy-2-aminobenzene 0.05
1-Hydroxy-4-aminobenzene 0.09
6-Hydroxybenzomorpholine 0.017
1-.beta.-Hydroxyethyloxy-2,4-diaminobenzene, dihydrochloride 0.039
Propylene glycol monobutyl ether 2.5
Pure monoethanolamine 1.06
Aqueous ammonia (containing 20.5% of ammonia). 11.1
Water qs
100
AS* = Active Substance
[0364] The dyeing composition was mixed, at the time of use, in a plastic
bowl and for 2 minutes, with the oxidizing composition given above, in an
amount of 1 part of dyeing composition per 1.5 parts of oxidizing
composition. The mixture obtained was applied to locks of natural grey
hair which is 90% white and allowed to act for 30 minutes. The locks were
then rinsed with water, they were washed with
shampoo and again rinsed
with water, and then dried and disentangled. The hair was then dyed in an
intense light chestnut brown shade.
[0365] Results of the same type were obtained by replacing, in the above
example, Aculyn 44 with 0.5% AS of Quatrisoft LM 200 sold by the company
AMERCHOL or with 0.5% AS of Pure Thix HH sold by the company SUD CHEMIE.
* * * * *